Past, Present, and Future of
Crystallography@Politecnico di Milano
From Small Molecules to Macromolecules
and Supramolecular Structures
Book of Abstracts
6-7 June, 2013
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
“ ... Milan Politecnico ... has seen a lot of crystallography. So there is a very nice
past; the present certainly is very well known in my own subject ... and the future,
you know, who knows what the future will bring? As I said, crystallographers and
people who use crystallography need to have a very, very open mind about what the
subject means.
”
Gautam R. Desiraju
President of the International Union of Crystallography
6 June 2013, Opening remarks to the Conference
6-7 June 2013, Milan, Italy
I
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
6-7 June 2013, Milan, Italy
II
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
In 2013 the Politecnico di Milano celebrated its 150th anniversary (1863-2013). 2013 also marked
the 50th anniversary of the award of the Nobel Prize in chemistry to Giulio Natta, for his discoveries
at the Politecnico di Milano in the field of the chemistry and technology of high polymers.
In this framework, the conference “Past, Present and Future of Crystallography@Politecnico di
Milano: From Small Molecules to Macromolecules and Supramolecular Structures” was held on 67 June, 2013 at Politecnico di Milano. The event celebrated the two above mentioned important
milestones for Chemistry and for our university.
The conference brought together leading scientists with interests in crystallography and crystal
engineering, providing an excellent opportunity to disseminate the latest results in the field.
ORGANIZING COMMITTEE
Pierangelo Metrangolo, Politecnico di Milano
Giuseppe Resnati, Politecnico di Milano
Gabriella Cavallo, Politecnico di Milano
Giancarlo Terraneo, Politecnico di Milano
SCIENTIFIC SECRETARIAT
Johanna Syvanen, Politecnico di Milano
6-7 June 2013, Milan, Italy
III
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
6-7 June 2013, Milan, Italy
IV
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Past, Present and Future of Crystallography@Politecnico di Milano:
From Small Molecules to Macromolecules and Supramolecular Structures
Organized under the auspices of:
IUCr (IYCr 2014)
AIC
AICIng
In collaboration with:
FluorIT
Sponsored by:
IUPAC
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
ACS
RSC
CrystEngComm
Bruker
Sigma Aldrich
Fondazione Cariplo
Politecnico di Milano
DCMIC
6-7 June 2013, Milan, Italy
VI
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
SCIENTIFIC PROGRAM
ORAL PRESENTATION - THURSDAY, JUNE 6, 2013
SESSION I – Chairman: Kari Rissanen
LIQUID ENGINEERING TO CRYSTAL ENGINEERING: HOW IONIC
LIQUIDS CAN HELP US MASTER THE PHARMACEUTICAL SOLID STATE
R. D. Rogers, S. P. Kelley
p. 11
LIQUID-CRYSTAL ENGINEERING: FROM MOLECULES TO MATERIALS
A. Crispini, D. Pucci, N. Godbert, M. La Deda, I. Aiello, M. Ghedini
p. 12
CRYSTAL ENGINEERING OF PHARMACEUTICAL CO-CRYSTALS
V. Ferretti
p. 13
SESSION II – Chairman: Giuseppe Resnati
SMART(LY DESIGNED) MATERIALS
M. J. Zaworotko
p. 16
INTERMOLECULAR INTERACTIONS IN MOLECULE-BASED MAGNETS:
LONG-DISTANCE BONDS BETWEEN RADICAL-IONS
M. Fumanal, M. Capdevila, J. S. Miller, J. J. Novoa
p. 17
ORGANIC MACROCYCLES FOR DESIGNING POROUS MATERIALS
C. Tedesco
p. 18
SESSION III – Chairman: Mir Wais Hosseini
CRYSTALLOGRAPHY OF LARGE SUPRAMOLECULAR COMPLEXES
K. Rissanen
p. 20
CRYSTALLOGRAPHY AND SUPRAMOLECULAR SENSING
C. Massera, E. Biavardi, R. Pinalli, F. Ugozzoli, E. Dalcanale
p. 21
NETWORK ANALYSIS IN CRYSTAL ENGINEERING, MORE THAN A DULL
TAXONOMY EXERCISE
L. Öhrström
p. 22
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
MOLECULAR RECOGNITION OF SMALL GUESTS BY CRYSTALLINE
SUPRAMOLECULAR
SYSTEMS:
FROM
LOCAL
CONTROL
TO
COLLECTIVE BEHAVIOUR…AND BACK
A. Bacchi, P. Pelagatti
p. 23
SESSION IV – Chairman: Robin D. Rogers
CRYSTALS,
p. 26
STRUCTURE-BASED SOLID-STATE FORM DESIGN: IDENTIFYING
COMMERCIALLY-VIABLE CRYSTAL FORMS FOR HIGH QUALITY DRUG
PRODUCTS
S. M. Reutzel-Edens
p. 27
MULTIPLE CRYSTAL FORMS: SWORD OF DAMOCLES OR AN
OPPORTUNITY FOR THE PHARMA INDUSTRY?
F. Grepioni
p. 28
POROSITY IN FLEXIBLE METAL-ORGANIC SYSTEMS
L. Barbour
p. 29
CRYSTALLOGRAPHY AND BIOMINERALIZATION: ON
DISORDERED PHASES, AND THEIR TRANSFORMATIONS
L. Addadi, A. Akiva, D. Gur, A. Gal, S. Weiner
ORAL PRESENTATION - FRIDAY, JUNE 7, 2013
SESSION V – Chairman: Mike Zaworotko
SELF-ASSEMBLIES FOR BIOMIMETIC MATERIALS
O. Ikkala
p. 32
POROUS COORDINATION NETWORKS: STRUCTURES, ENTANGLEMENTS
AND PROPERTIES
L. Carlucci, G. Ciani, D. M. Proserpio
p. 33
RECOGNITION AND SENSING
STRUCTURAL ASPECTS
P. Paoli
p. 34
6-7 June 2013, Milan, Italy
WITH
POLYAMINE-BASED
HOSTS:
2
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
SESSION VI – Chairman: Pierangelo Metrangolo
FROM TECTONS TO CRYSTALS OF CRYSTALS
M. W. Hosseini
p. 36
AT THE LIMITS OF IN SITU CRYSTALLIZATION FOR STRUCTURE
DETERMINATION
R. Boese
p. 37
IN
SITU
CRYOCRYSTALLIZATION
OF
HALOGEN
SUPRAMOLECULAR COMPLEXES
G. Terraneo, G. Cavallo, T. Pilati, P. Metrangolo, G. Resnati
BONDED
p. 39
CRYSTAL
p. 40
FLUORINE AND DEUTERIUM:
ARCHITECTURE.
V. Vasylyeva, K. Merz, O. V. Shishkin
6-7 June 2013, Milan, Italy
INFLUENCE
ON
THE
3
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
6-7 June 2013, Milan, Italy
4
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
POSTERS
P1
SUPRAMOLECULAR INTERACTIONS AS GLUE FOR THE DESIGN OF
SMART ARCHITECTURES
I. Bassanetti, A. Comotti, S. Bracco, L. Marchio, P. Sozzani
p. 42
P2
POROUS DIPEPTIDE CRYSTALS AND ORGANIC FRAMEWORKS AS
POLYMERIZATION VESSELS
M. Beretta, A. Comotti, S. Bracco, P. Sozzani
p. 43
P3
NEW HYBRID ORGANIC-ORGANOMETALLIC NANO-RIBBONS
R. Bertani, P. Sgarbossa, V. Di Noto, M. Piga, G. Giffin, G. Terraneo, T. Pilati, P.
Metrangolo, G. Resnati
p. 44
P4
SYNTHESIS OF A COUMARIN - NBD CALIX[4]ARENE SYSTEM AND
SPECTROSCOPIC STUDY OF ITS ENERGY TRANSFER PROPERTIES
I. Tosi, L. Baldini, S. Bertella, F. Sansone, F. Terenziani
p. 45
P5
X-RAY DIFFRACTION IS THE EXPERIMENTAL ARM OF
CRYSTALLOGRAPHY. KNOWN AND UNKNOWN TRIBUTE OF PISA
FROM LAST TOWARDS NEXT TWENTIES
G. Berti, F. De Marco, S. Aldrighetti
p. 46
P6
THE
EFFECT
OF
THE
FLUORINE
SUBSTITUTION
ON
SUPRAMOLECULAR ASSEMBLIES OF ARYL BENZYL SULFOXIDES
C. Cardellicchio, M. A. M. Capozzi, F. Capitelli
p. 47
P7
ACTIVATION OF ROOM TEMPERATURE PHOSPHORESCENCE OF
ORGANIC CO-CRYSTALS.
A NOVEL APPROACH BASED ON HALOGEN-BOND.
L. Catalano, A. Bertocco, S. D'Agostino, B. Ventura, F. Grepioni, D. Braga
p. 48
P8
FLUORINATED
METAL-ORGANIC
FRAMEWORKS
ASSEMBLED VIA HALOGEN BOND
L. Colombo, P. Metrangolo, T. Pilati, G. Resnati, G. Terraneo
SELF-
p. 49
P9
CRYSTAL
STRUCTURE
AND
OPTICAL
PROPERTIES
OF
FLUORINATED PUSH-PULL J-AGGREGATES
V. Dichiarante, E. Cariati, G. Cavallo, A. Forni, P. Metrangolo, T. Pilati, G.
Resnati, G. Terraneo
p. 50
P10
DESMOTROPY, POLYMORPHISM AND SOLID-STATE PROTON
TRANSFER: FOUR SOLID FORMS OF AN AROMATIC O-HYDROXY
SCHIFF BASE
I. Ĉiloviü, M. Rubþiü, K. Užareviü, I. Halasz, N. Bregoviü, M. Mališ, Z. Kokan, R.
S. Stein, R. E. Dinnebier, V. Tomišiü
p. 51
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P11
DESIGN, SYNTHESIS AND CHARACTERIZATION OF LUMINESCENT
COPPER(I)-IODIDE COMPLEXES FOR OPTOELECTRONIC DEVICES
F. Farinella, P. P. Mazzeo, L. Maini, D. Braga
p. 52
P12
ORGANIC FRAMEWORKS FORMED VIA HYDROGEN AND HALOGEN
BONDING ORTHOGONAL SELF-ASSEMBLY
F. Fernandez-Palacio, L. Colombo, J. Martí-Rujas, G. Terraneo, T. Pilati, P.
Metrangolo, G. Resnati
p. 53
P13
LCDIXRAY: POWDER DIFFRACTION INDEXING OF COLUMNAR
LIQUID CRYSTALS
N. Godbert, A. Crispini, M. Ghedini, M. Carini, F. Chiaravalotti, A. Ferrise
p. 54
P14
REAL-TIME IN SITU X-RAY DIFFRACTION MONITORING OF
MECHANOCHEMICAL
FORMATION
OF
MODEL
ORGANIC
PHARMACEUTICAL COCRYSTAL
I. Halasz, A. Puškariü, S. A. J. Kimber, P. J. Beldon, F. Adams, V. Honkimäki, R.
E. Dinnebier, V. Štrukil, T. Frišþiü
p. 55
P15
STRUCTURAL STUDIES OF SUPRAMOLECULAR GYROSCOPE-LIKE
CO-CRYSTALS
J. Lin, C. M. Widdifield, G. Cavallo, G. A. Facey, T. Pilati, P. Metrangolo, G.
Resnati, D. L. Bryce
p. 56
P16
ON THE ROLE OF HYDROGEN BOND IN THE CRYSTAL PACKING OF
RU (II) HALF-SANDWICH COMPLEXES
C. Loffi, P. Pelagatti, A. Bacchi, P. Swuec
p. 57
P17
A VOYAGE IN THE B VITAMINS WORLD: B6 AS NOVEL LIGAND IN
CLUSTER CHEMISTRY AND NEW DISCOVERIES IN THE FIELD OF
B12 CRYSTALLOGRAPHY.
N. Marino, D. Armentano, G. De Munno, R. P. Doyle
p. 58
P18
SUPRAMOLECULAR GELS FORMATION INDUCED BY HALOGEN
BONDING
L. Meazza, J. A. Foster, K. Fucke, P. Metrangolo, G. Resnati, J. W. Steed.
p. 59
P19
POLYMORPHISM AND SOLID FORMS IN 1,1,4,4-TETRAPHENYL-1,3BUTADIENE.
A. Monica, A. Bacchi, M. Masino, D. Crocco
p. 60
P20
PICTURING THE INDUCED FIT OF CALIX[5]ARENES UPON
N-ALKYLAMMONIUM CATION BINDING
A. Notti, G. Gattuso, S. Pappalardo, M. F. Parisi, T. Pilati, G. Resnati, G. Terraneo
p. 61
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P21
TRAVELLING
WITH
POLYMORPHS:
THE
CASE
OF
TETRAPENTOXYCALIX[4]ARENE
A. G. Ricciardulli, M. Lusi, L. Erra, C. Gaeta, C. Talotta, P. Neri, L. J. Barbour, C.
Tedesco
p. 62
P22
FUNCTIONAL GROUP EFFECT ON THE CLATHRATING PROPERTIES
OF HALF-SANDWICH RU (II) COMPLEX
F. Scè, A. Bacchi, P. Pelagatti
p. 63
P23
PT(II)-IMINO DERIVATIVES: DIMERS AND OLIGOMERS AS A
SUPPLY OF CYTOTOXIC AGENTS
P. Sgarbossa, R.A. Michelin, R. Bertani, M. Mozzon, C. Marzano, V. Gandin
p. 64
P24
ZNO
NANOPARTICLES
SYNTHESIS
WITH
CONTROLLED
MORPHOLOGY
(SHAPE
&
SIZE)
BY
USING
NATURAL
BIODEGRADABLE POLYMER
S. U. Shisodia, A. Citterio, V. V. Chabukswar, N. S. Pande, V. Purohit, S. V.
Bhavsar, K. N. Hondore, K. C. Mohite
p. 65
P25
CRYSTALLIZATION OF TWO ISOMERIC AMINOACIDS FROM
SOLUTION AND FROM GEL
F. Silvestri, D. Crocco, A. Bacchi
p. 66
P26
A NANOPOROUS CRYSTALLINE STRUCTURE GENERATED BY A
TIOUREA-BASED CALIX[6]ARENE
F. Ugozzoli, A. Arduini, R. Bussolati, C. Massera, F. Rapaccioli, A. Secchi
p. 67
P27
SELECTIVE MECHANOCHEMISTRY: FLEXIBLE MOLECULAR
RECEPTORS FOR RECOGNITION OF ORGANIC ISOMERS IN
MILLING PROCESSES
K. Užareviü, I. Halasz, I. Ĉiloviü, M. Rubþiü, N. Bregoviü
p. 68
POSTER PRIZE WINNERS
p. 70
AUTHOR INDEX
p. 74
6-7 June 2013, Milan, Italy
7
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
6-7 June 2013, Milan, Italy
8
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
ORAL PRESENTATIONS
6-7 June 2013, Milan, Italy
9
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
SESSION I
Chairman: Kari Rissanen
6-7 June 2013, Milan, Italy
10
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Liquid Engineering to Crystal Engineering:
How Ionic Liquids Can Help Us Master the Pharmaceutical Solid State
R. D. Rogers, S. P. Kelley
Center for Green Manufacturing and Department of Chemistry, The University of Alabama,
Tuscaloosa, Alabama 35487, USA
E-mail address: [email protected]
The pharmaceutical industry relies mainly on the solid forms of active pharmaceutical ingredients
(APIs) for drug delivery, which has resulting in increasing instances of problems such as
polymorphic conversion, low solubility, and low bioavailability which are associated with solid
compounds. This has led to a major effort to create marketable new drugs by improving the
properties of already known APIs by designing new solid forms through strategies such as salt
formation, co-crystallization, and polymorph screening, but these approaches have brought new
challenges such as the regulatory classification of multicomponent solids which are neither
completely ionic nor completely neutral. However, the strategy of avoiding the solid state entirely
through the use of low melting salts (ionic liquids, or ILs) has received less attention. ILs are highly
tunable liquids which have been applied to drug delivery through strategies ranging from solvating
and dispersing agents for poorly soluble drugs to bypassing the solid state altogether by making API
salts into compounds that form neat liquids at low temperatures.
It is time for the pharma sector to learn more about the potential impact of ILs in virtually every
phase of drug discovery, manufacture, and delivery. A more fundamental, systems view of ILs is
needed to overcome hesitation in using them by obtaining an appreciation of the true power of IL
design to purpose. ILs have utility in the manufacture of APIs, delivery of APIs, and even as APIs.
IL APIs even have a role in expanding the understanding of crystal engineering as they offer a
dynamic liquid environment in which to study the effects of ionicity on the physicochemical
properties of a neat API compound as a complement to the solid state. In this presentation, several
aspects of the IL form of matter will be discussed to illustrate the broad utility of these materials in
the pharma industries which can be realized by adopting an ‘Ionic Liquid’ way of thinking.
Figure 1: Roles of ILs throughout the API design and delivery process
6-7 June 2013, Milan, Italy
11
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Liquid-Crystal Engineering: From Molecules to Materials
1
A. Crispini1, D. Pucci1, N. Godbert1, M. La Deda1, I. Aiello1, M. Ghedini1
Department of Chemistry and Chemica Technologies , University of Calabria, Italy.
E-mail: [email protected]
The self-assembly of suitable building-blocks, through inter- or intra-molecular interactions of
different nature, is a current approach to get new nanostructure materials, amongst which liquid
crystals are particularly intriguing due to their ordered yet dynamic structures [1]. The synthesis of
liquid crystals based on metal complexes (metallomesogens) has received great attention since the
metal centre is able to promote mesomorphism in non mesogenic ligands. Significant progress has
been made in the field of metallomesogens, by modulating factors such as nano-segregation,
molecular motifs functional to specific intermolecular interactions and molecular shapes [2]. In this
context, we have devoted our studies towards the careful choice of various molecular frameworks in
the modulation of interactions responsible for the supramolecular architectures suitable in metalcontaining liquid crystalline molecular materials [3]. This communication will illustrate examples
chosen from our library of metallomesogens, proving our liquid-crystal engineering approach in the
modulation of molecular shape (by changing the metal ions and the organic ligands) and non
covalent interactions (by changing substituents on the molecular organic fragments). A deep study
of their molecular organization both in the crystalline solid state and the liquid crystalline phases,
conducted through single crystal and variable temperature powder X ray analyses, will be presented
in order to highlight the relationships between structure and mesomorphic behaviour based on non
covalent interactions.
Figure 1: PXRD pattern of an unconventional Pd-mesogen in its hexagonal phase and derived crystal packing [3]
References
1. T. Kato, Chem. Commun., 2009, 729.
2. Metallomesogens In Comprehensive Coordination Chemistry II: From Biology to Nanotechnology, Vol.
7 (Eds.: J. A. McCleverty, T. J. Meyer, M. Fujita, A. Powell) Elsevier, Oxford, 2003, ch. 7.9, pp. 357-627
3. D. Pucci, I. Aiello, A. Aprea, A. Bellusci, A. Crispini and M. Ghedini, Chem. Commun., 2009, 1550; D.
Pucci, A. Crispini, M. Ghedini, E. I. Szerb, M. La Deda, Dalton Trans., 2011, 40, 4614.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Crystal Engineering of Pharmaceutical Co-crystals
V. Ferretti
Department of Chemical and Pharmaceutical Sciences and Centre for Structural Diffractometry,
University of Ferrara, via L. Borsari 46, I-44121 Ferrara, Italy
E-mail: [email protected]
In the last years, the design and synthesis of co-crystals containing active pharmaceutical
ingredients (APIs) has become the new frontier of the crystal engineering due to the great
opportunity to modify the physico-chemical properties of solid forms of drugs. Actually, the
pharmaceutical co-crystals display intermolecular motifs and hence crystal structure different from
the pure API component, and consequently can exhibit diverse specific physical properties, such as
solubility and dissolution rate; this makes it possible to hypothesize interesting influences in the
bioavailability or local delivery of the drug itself.
An efficient preparation of desired cocrystals requires an understanding and exploitation of the
intermolecular interactions which may occur between the API and the other crystal co-formers in
order to obtain robust supramolecular synthons. Relying on our long experience in the study of
intermolecular interactions (in particular hydrogen bonding) and of co-crystals in general, we have
started a project of supramolecular synthesis using different APIs and aromatic bases. In this
communication the focus will be on cocrystals containing phloroglucinol (an example is shown in
Fig.1), an antispasmodic agent, carbamazepine, an anticonvulsant, and indomethacin, a nonsteroidal anti-inflammatory drug. Besides a detailed investigation of the characteristic behaviour of
the coformers’ functional groups (mostly hydrogen bonding donors or acceptors) and their influence
on the crystal structures and packing motifs, the solubility and dissolution rate of some
indomethacin cocrystals have been evaluated.
Figure 1: The hydrogen bonding pattern for phloroglucinol/tetramethyl-pyrazine co-crystal.
6-7 June 2013, Milan, Italy
13
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
6-7 June 2013, Milan, Italy
14
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
SESSION II
Chairman: Giuseppe Resnati
6-7 June 2013, Milan, Italy
15
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Smart(ly Designed) Materials
1
M. J. Zaworotko1
University of South Floruida, Tampa, USA
E-mail: [email protected]
That composition and structure profoundly impact the properties of crystalline solids has provided
impetus for exponential growth in the field of crystal engineering [1]. Strategies for the generation
two classes of multi-component crystalline materials will be addressed:
x Pharmaceutical cocrystals [2] have emerged at the preformulation stage of drug development
because their modular and designable nature facilitates discovery of new crystal forms of active
pharmaceutical ingredients with changed physicochemical properties. We shall address the
profound impact that cocrystallization can have upon solubility and bioavailability by
presenting a case study.
x Metal-Organic Materials (MOMs) that are built from metal or metal cluster “nodes” and
organic “linkers” have captured the imagination of materials scientists because they are
amenable to crystal engineering and they offer unprecedented levels of porosity. Two families
of MOMs are currently of interest to our group: Porph@MOMs in the context of gas storage
and catalysis [3]. Pillared grids (see Figure 1) afford unprecedented selectivity for carbon
capture in narrow pore MOMs [4].
In summary, this lecture will emphasize how crystal engineering has reached the “end of the
beginning”, a rather exciting point in time since crystal engineering offers a paradigm shift from the
more random, high-throughput methods that have traditionally been utilized in materials discovery
and development.
Figure 1: A schematic representation of a pillared grid framework (reference 4)
References
1. (a) G.R. Desiraju, Crystal engineering: The design of organic solids Elsevier, 1989; (b) B. Moulton, M.J.
Zaworotko, Chemical Reviews 2001, 101, 1629-1658.
2. P. Vishweshwar, J.A. McMahon, J.A. Bis, M.J. Zaworotko, J. Pharm. Sci. 2006, 95, 499-516.
3. Z.Z. Zhang, L. Zhang, L. Wojtas, P. Nugent, M. Eddaoudi, M.J. Zaworotko, J. Amer. Chem. Soc. 2012,
134, 924-927.
4. (a) S.D. Burd, S. Ma, J.A. Perman, B.J. Sikora, R.Q. Snurr, P.K. Thallapally, J. Tian, L. Wojtas, M.J.
Zaworotko, J. Amer. Chem. Soc. 2012, 134, 3663-3666. (b) M. Mohamed, S. Elsaidi, J. Wojtas, T. Pham,
K.A. Forrest, B. Tudor, B. Space, M.J. Zaworotko, J. Amer. Chem. Soc., 2012, 134, 19556-19559. (c) P.
Nugent, Y. Belmabkhout, S.D. Burd, A.J. Cairns, R. Luebke, K.A. Forrest, T. Pham, S Ma, B. Space, L.
Wojtas, M. Eddaoudi, M.J. Zaworotko, Nature, 2013, 495, 80-84.
6-7 June 2013, Milan, Italy
16
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Intermolecular interactions in molecule-based magnets: Long-distance bonds
between radical-ions
a
M. Fumanal,a M. Capdevila,a J. S. Miller,b J. J. Novoaa
Dept. Química Física & IQTCUB, Fac. Química, Univ. Barcelona Av. Diagonal, 645, 08028Barcelona (Spain)
b
Department of Chemistry, University of Utah, Salt Lake City, UT 84112-0850, USA
E-mail: [email protected]
Molecule-based crystals presenting magnetic properties show a rich polymorphism whose magnetostructural properties are not yet fully understood. A key factor for such limitation is the lack of a
proper understanding of the energetic and magnetic properties of the radical•••radical interactions
due to their combined bonding-electrostatic-dispersive character. This situation is particularly true
when the molecule-based magnet presents radical-ions, in their structure.
In some of these molecule-based magnets presenting radical-ions, the magnetic properties can only
be explained by considering the formation of diamagnetic radical-ion•••radical-ion pairs. Despite the
large separation of the radicals in these pairs, ~3 Å or larger, these pairs share most of the properties
of covalent bonds, except their intrinsic stability (in most cases, they are metastable). However,
these radical-ions pairs become energetically stable in room temperature solids, due to the
combined effect of the radical-ion•••counterion interactions. They are also stable in various
solutions, up to about -40 ºC, due to the combined impact of the radical-ion•••solvent interactions.
This allows to talk about the presence of long, multicenter bonds between these radicals. 1,2
In this work we present the theoretical and experimental evidence concerning these bonds in pairs
of radical-anions, radical-cations, and neutral radicals pairs. They are also found in radicalcation•••radical-anion pairs. Recent experimental results concerning the presence of these dimers in
room temperature solution are also analyzed.
References
1. (a) Novoa, J. J.; Lafuente, P.; Del Sesto, R. E.; Miller, J. S. Angew. Chem. Int. Ed. 2001, 40, 2540; (b) Del
Sesto, R. E.; Miller, J. S.; Lafuente, P.; Novoa, J. J. Chem. Eur. J. 2002, 8, 4894; (c) Novoa, J. J.;
Lafuente, P.; Del Sesto, R. E.; Miller, J. S. CrystEngComm 2002, 4, 373.
2. Miller, J. S.; Novoa, J. J. Acc. Chem. Res. 2007, 40, 189.
6-7 June 2013, Milan, Italy
17
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Organic macrocycles for designing porous materials
C. Tedesco1
Dipartimento di Chimica e Biologia, Università degli Studi di Salerno,Fisciano (SA), Italy
E-mail: [email protected]
The development of self-assembled solid-state supramolecular architectures with nanosized pores or
cavities is an intensively active research area, aiming at the preparation of new materials with
potential applications in nanotechnology such as molecular sieves, sensors, and gas-storage devices.
Organic solids could represent a competing alternative to zeolites, clays, metal-organic frameworks,
mesoporous metal oxides. They feature not only the required porosity but also high selectivity,
which can be achieved both by tailoring channel dimensions to guest molecules, and also by
providing specific interactions with organic functional groups. Moreover, dynamic structural
transformations based on flexible porous frameworks are always possible leading to functional
materials with the fabrication of switches or actuators at a supramolecular level.
Two types of macrocycles will be considered, namely calixarenes and cyclopeptoids. Both represent
a class of very versatile compounds, which can be easily modified to achieve the desired building
blocks. While cyclopeptoids constitute a class of relatively new compounds, whose properties are
still unexplored [1,2], calixarenes have been successfully employed to obtain porous nanostructured
materials.[3-8] Examples of the solid state assembly of both class of compounds will be reported to
show their extreme versatility as building blocks for designing new materials.
Figure 1: Two sodium ions and one cyclopeptoid molecule are linked to form a 1D polymer structure.
References
1. N. Maulucci, I. Izzo, G. Bifulco, A. Aliberti, C. De Cola, D. Comegna, C. Gaeta, A. Napolitano, C. Pizza,
C. Tedesco, D. Flot, F. De Riccardis, ChemComm. 2008, 3927-3929.
2. I. Izzo, G. Ianniello, C. De Cola, B. Nardone, L. Erra, G. Vaughan, C. Tedesco, F. De Riccardis, Org.
Lett. 2013, 15, 598-601.
3. C. Tedesco, I. Immediata, L. Gregoli, L. Vitagliano, A. Immirzi, P. Neri, CrystEngComm 2005, 7, 449453.
4. P. K. Thallapally, B. P. McGrail, J. L. Atwood, C. Gaeta, C. Tedesco, P. Neri, Chem. Mater. 2007, 19,
3355-3357.
5. C. Tedesco, L. Erra, M. Brunelli, V. Cipolletti, C. Gaeta, A. N. Fitch, J. L. Atwood, P. Neri, Chem. Eur.
J. 2010, 42, 2371-2374.
6. L. Erra, C. Tedesco, V. R. Cipolletti, L. Annunziata, C. Gaeta, M. Brunelli, A. N. Fitch, C. Knöfel, P.L.
Llewellyn, J. L. Atwood, P. Neri, Phys. Chem. Chem. Phys. 2012, 14, 311-317.
7. C. Tedesco, L. Erra, I. Immediata, C. Gaeta, M. Brunelli, M. Merlini, C. Meneghini, P. Pattison, P. Neri,
Cryst. Growth Des. 2010, 10, 1527-1533.
8. L. Erra, C. Tedesco, I. Immediata, L. Gregoli, C. Gaeta, M. Merlini, C. Meneghini, M. Brunelli, A. N.
Fitch, P. Neri, Langmuir 2012, 28, 8511-8517.
6-7 June 2013, Milan, Italy
18
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
SESSION III
Chairman: Mir Wais Hosseini
6-7 June 2013, Milan, Italy
19
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Crystallography of Large Supramolecular Complexes
K. Rissanen
Department of Chemistry, Nanoscience Center, University of Jyväskylä,
40014 JYU Jyväskylä, Finland
E-mail: [email protected]
An exciting research challenge in supramolecular chemistry is to design, synthesize, and
characterize nano-sized architectures with applications in biology, chemistry, and materials
science.[1] Predicting and designing non-covalently bound supramolecular complexes and
assemblies is difficult because of the weakness of the interactions involved, thus the resulting
superstructure is often a compromise between the geometrical constraints of the building blocks and
the competing weak intermolecular interactions.[2]
Our research interest has been focused on the studies of
weak non-covalent intermolecular, viz. supramolecular
interactions as the driving force in self-assembly and molecular
recognition, especially in the solid state by single crystal X-ray
diffraction. The most recent studies have focused on hydrogen[3]
and halogen[4] bonded systems, i- i [5], CH…anion [6], and
anion… i[7] interactions and metal ion coordination[8] in
molecular self-assembly and molecular recognition in various
systems such a resorcinarenes, ditopic receptors, rotaxanes, M4L6
tetrahedra, M8L6 cube, spheres, knots, etc.. The lecture will
highlight some crystallographic studies
of large (FW > 5000) supramolecular complexes.
Fig. 1. The X-ray structure of
the pentafoil knot. [8b]
References
1. F. Hof, L.S. Craig, C. Nuckolls, J. Rebek Jr, Angew. Chem. Int. Ed. 2002, 1488-1451.
2. a) G.R. Desiraju Nature, 2001, 397-399. b) T. Steiner, Angew. Chem. Int. Ed. 2002, 41.
3. N. Kodiah Beyeh, M. Cetina, K. Rissanen, Cryst. Growth Des. 2012, 4919 - 4926.
4. a) K. Raatikainen, K. Rissanen, Chem. Sci. 2 (2012), 1235–1239. b) K. Raatikainen, K. Rissanen,
CrystEngComm 2011, 6972 – 6977. c) P. Metrangolo, Y. Carcenac, M. Lahtinen , T. Pilati, K. Rissanen,
A. Vij, G. Resnati, Science 2009, 1461-1464.
5. a) H. Mansikkamäki, M. Nissinen, K. Rissanen, Angew. Chem. 2004, 1263-1265. b) H. Mansikkamäki, S.
Busi, M. Nissinen, A. Åhman, K. Rissanen, Chem. Eur. J. 2006, 4289.
6. S.S. Zhu, H. Staats, K. Brandhorst, J. Grunenberg, F. Gruppi, E. Dalcanale, A. Lützen, K. Rissanen, C.A.
Schalley, Angew. Chem. Int Ed. 2008, 788-792.
7. a) M. Giese, M. Albrecht, T. Krappitz, M. Peters, V. Gossen, G. Raabe, A. Valkonen, K. Rissanen, Chem.
Comm. 48 (2012), 9983 – 9985. b) M. Albrecht, C. Wessel, M. de Groot, K. Rissanen, A. Lüchow A, J.
Am. Chem. Soc. 2008, 4600.
8. J. Bunzen, J. Iwasa, P. Bonakdarzadeh, E. Numase, K. Rissanen, S. Sato, M. Fujita, Angew. Chem. 2012,
3161 - 3163. b) J.-F. Ayme, J. E. Beves, D. A. Leigh, R. T. McBurney, K. Rissanen, D. Schultz, Nat.
Chem. 2012, 15 – 20. c) W. Meng, B. Breiner, K. Rissanen, J. D. Thoburn, J. K. Clegg, J. R. Nitschke,
Angew. Chem. 2011, 3479 - 3483. d) P. Mal, B. Breiner, K. Rissanen, J. R. Nitschke, Science 2009, 1697
- 1698.
6-7 June 2013, Milan, Italy
20
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Crystallography And Supramolecular Sensing
C. Massera, E. Biavardi, R. Pinalli, F. Ugozzoli, E. Dalcanale
Dipartimento di Chimica, Parco Area delle Scienze 17/A, 43124 Italy
E-mail: [email protected]
The demand for fast and reliable detection of biological and chemical hazards as well as rapid and
accurate diagnosis of diseases is continuously rising because of their foremost relevance in global
health. Optimal sensors for environmental, security and biomedical applications must be
sufficiently responsive to allow detection of the target analyte at low concentrations, and selective
enough to respond primarily to a single chemical species in presence of interferents. In this respect
resorcinarene-based cavitands, synthetic organic compounds with enforced cavities of molecular
dimensions, represent a very important class of receptors for chemical and biochemical sensing [1].
In the design of cavitands, the choice of the bridging groups connecting the phenolic hydroxyls of
the resorcinarene scaffold is pivotal, since it determines shape, dimensions and complexation
properties of the resulting cavity. In this way the molecular recognition approach can be
implemented using ad hoc synergic host-guest interactions to achieve the desired selectivity
towards different types of analytes [2, 3].
In the case of aromatic guests, quinoxaline-bridged (QxCav) and linked quinoxaline-bridged
(QxBox) cavitands have proved to be extremely effective receptors through the formation of S-S
stacking and CH-S interactions (Figure 1).
Figure 1: Molecular structure of the complex formed between the cavitand QxBox and benzene.
In this framework, single-crystal X-ray analysis on the resulting complexes is an extremely
important diagnostic tool because it provides precise information on the type, number, strength and
geometry of the weak interactions responsible for host-guest association in the solid state, allowing
to predict the sensor behavior.
References
1. D. J. Cram, Science, 1983, 219, 1177-1183.
2. R. Pinalli, M. Suman, E. Dalcanale, Eur. J. Org. Chem., 2004, 451-462.
3. L. Pirondini, E. Dalcanale, Chem. Soc. Rev., 2007, 36, 695-706.
6-7 June 2013, Milan, Italy
21
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Network Analysis in Crystal Engineering, More than a Dull
Taxonomy Exercise
1
L. Öhrström1
Chalmers Tekniska Högskola, Dept. of Chemical and Biological Engineering, Göteborg, Sweden
E-mail: [email protected]
At a first glance, analysis of network topologies,[1] deals with chemical objects that have already
been created and might thus superficially be dismissed as nomenclature exercises of little value to
the creative chemist. However, rejecting this as mere workout in taxonomy is completely wrong, as
opportunities of a deeper understanding and of an efficient presentation may be lost in the process.
Moreover, this approach also has a forward looking component, enabling us to design solid state
molecule-based materials, thus to do crystal engineering.
There are four important reasons for finding out the network topology of a crystal structure, be
this a Metal-Organic Framework, Coordination Polymer or a hydrogen bonded system: 1. To
understand the products we have. 2. To compare these materials to what others have made. 3. To
efficiently communicate our results to colleagues. 4. To truly make something new by design.
That the method is widely applicable is illustrated below by the new tetragonal allotrope of the
group 14 elements, the “T12” phase.[2] This allotrope was proposed based on elaborate
computational methods, accounting for some experimental results in synthesized metastable phases
but could easily have been predicted by the analysis of network topologies with appropriate
geometrical constraints.[3]
Figure 1. The Si T12 phase (left, Reprinted with permission from Zhao, Z.; Tian, F.; Dong, X.; Li, Q.; Wang, Q.; Wang,
H.; Zhong, X.; Xu, B.; Yu, D.; He, J.; Wang, H.-T.; Ma, Y.; Tian, Y. J. Am. Chem. Soc. 2012, 134, 12362. © (2012) the
American Chemical Society) and the ideal cdp net from the RCSR database.
1. A. F. Wells, Acta Cryst. 1954, 7, 535-544.
2. Z. Zhao, F. Tian, X. Dong, Q. Li, Q. Wang, H. Wang, X. Zhong, B. Xu, D. Yu, J. He, H.-T. Wang, Y.
Ma, Y. Tian, J. Am. Chem. Soc. 2012, 134, 12362-12365.
3. L. Öhrström, M. O'Keeffe, Z. Kristallogr. in press 2013.
6-7 June 2013, Milan, Italy
22
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Molecular recognition of small guests by crystalline supramolecular systems:
from local control to collective behaviour…and back
A. Bacchi, P. Pelagatti
Dipartimento di Chimica, University of Parma, Italy
E-mail: [email protected]
The complete control over the fabrication of crystalline materials is nowadays inspired to a bottomup philosophy that ideally starts with the design and synthesis of good building blocks for
assembling a functional material, proceeds with the prediction of how molecular units will selfassemble in the crystal, deals with the nucleation of the correct crystal form, the growth of final
materials with a predetermined shape, and ultimately relates macrolevel properties to the geometry
and strength of intermolecular interactions. The full toolkit of crystal engineering is here used to
rationalize the design of responsive metalloorganic materials with flexible dynamic frameworks,
able to create pores on demand to accommodate small guest molecules [1]. Emphasis is put on the
possibility to proceed from local design to the control of collective behaviour; this aim is achieved
by a careful chemical tailoring of the molecular species built by coordinating organic ligands to
metallo-organic moieties to obtain molecules with a predetermined shape. A careful design of both
the inorganic unit and the ligands that constitute the molecular skeleton is illustrated, aimed to
finely tune the supramolecular properties of the crystalline frameworks. Based on the number of
hydrogen bond donors and acceptors and on their nature materials exhibiting a range of inclusion
propensities are reviewed, from stiff networks that do not include any guest to extremely dynamic
materials that easily transform in the solid state to exchange guests by solid/vapour and solid/liquid
processes.
In this lecture we also explore the fascination of the reverse approach [2]: we analyze and measure
the macroscopic morphologies obtained from different solvents of a single organometallic
compound in order to identify and rank the intermolecular forces responsible for molecular self
recognition on one hand, and to test and quantify how the different functional groups interact with
different solvents on the other.
Figure 1. From supramolecular synthons to macroscopic properties (left)…and back (right).
References
1. A. Bacchi, M. Carcelli, P.Pelagatti, Crystall. Rev. 2012, 18, 253-279.
2. A. Bacchi, G. Cantoni, D. Cremona, P. Pelagatti, F. Ugozzoli,, Angew. Chem Int. Ed.., 2011, 50, 31983201.
6-7 June 2013, Milan, Italy
23
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
6-7 June 2013, Milan, Italy
24
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
SESSION IV
Chairman: Robin D. Rogers
6-7 June 2013, Milan, Italy
25
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Crystallography and biomineralization:
On crystals, disordered phases, and their transformations
L. Addadi, A. Akiva, D. Gur, A. Gal, S. Weiner
Dept of Structural Biology, Weizmann Institute of Science, Rehovot, Israel
E-mail: [email protected]
Biomineralization offers a plethora of beautiful examples of non conventional single crystals and
crystal assemblies with uniquely sculpted morphologies, and of stable and transient disordered
phases. Evolution has optimized their design, their properties and their mechanisms of formation to
adapt them to functions ranging from skeletal support to food grinding, soft tissue protection, light
manipulation, navigation and others.
We have been using the tools of crystallography to glean information on crystal properties including
crystallinity, stability, anisotropy and perfection, on crystal formation mechanisms and disorder-order
transitions. Examples that will be specifically discussed include bone and the formation pathway of
the carbonated hydroxyapatite crystals in bone from the cells to the collagen extracellular matrix [1], the
guanine-based photonic crystals providing iridescence to fish scales and skin and their formation
mechanism [2], and cystoliths, calcified objects composed of amorphous calcium carbonate which
function is increasing the yield of light utilization in the leaves of some plants [3].
References
1. J Mahamid, B Aichmayer, E Shimoni, R Ziblat, C Li, S Siegel, O Paris, P Fratzl, SWeiner, L Addadi,
PNAS 2010, 107, 6316–6321
2. D Gur, Y Politi, B Sivan, P Fratzl, S Weiner, L Addadi, Angew Chemie Int Ed 2012, 52, 388-391.
3. A Gal, A Hirsch, S Siegel, C Li, Y Politi, P Fratzl, S Weiner, L Addadi, Chem. Eur. J. 2012, 18, 10262 –
10270; A Gal, W Habraken, D Gur, P Fratzl, S Weiner, LAddadi Angew Chemie 2013, in press
6-7 June 2013, Milan, Italy
26
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Structure-based solid-state form design: Identifying commercially-viable crystal
forms for high quality drug products
S. M. Reutzel-Edens
Lilly Research Laboratories, Eli Lilly and Company, Indianapolis, IN U.S.A.
E-mail: [email protected]
The identification of commercially-viable solid-state forms is a key first step to ensuring that a drug
substance will meet the design requirements of the drug product. The process of identifying even
one suitable solid-state form can be lengthy and difficult, however. Fortunately, salt formation, and
more recently cocrystallization, greatly expand the options for engineering particles to desired
specifications. In this presentation, salts and cocrystals discovered through design and serendipity
are evaluated in the context of the ever-evolving solid form landscape, providing a useful
framework from which a solid form may be selected from potentially numerous options discovered
through solid-state form screening and the risks of physical instability may be understood.
Challenges in defining experimental solid form landscapes, ensuring that viable forms are not
missed, and the transferability of knowledge about form landscapes from those of structurallyrelated molecules, are discussed.
free energy
citrate salt
di-HCl salt
tartaric acid
cocrystal
phosphate salt
crystalline hit (initial screen)
stable f orm (comprehensive screen)
metastable crystal f orm
free base
amorphous f orm
fumarate salt
6-7 June 2013, Milan, Italy
27
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Multiple crystal forms: Sword of Damocles or an
opportunity for the pharma industry?
F. Grepioni
Università di Bologna, Dipartimento di Chimica Ciamician, Via Selmi 2, 40126 Bologna, Italy
E-mail: [email protected]
Rational design and construction of crystalline solids with predefined architectures and physical
properties starting from the choice of the molecular components, e.g. crystal engineering, is often
challenged by the fact that it is difficult to devise structure-property or structure-function
relationships with an acceptable degree of confidence when the end-product, the crystal, can be only
one of many.
Multiple crystal forms (co-crystals, molecular salts, solvates, polymorphs) are currently investigated
in the academic world because they provide new insights into mechanisms of recognition, assembly
and packing. In the pharmaceutical field, and in all areas where the final products are
commercialized and utilized in their solid state form, they are sought for and exploited as a means
to access new solid state properties. The practical consequences are enormous, as they impact on
the stability, processability, reproducibility, even transport and manufacture conditions, hence on
the market potentials, of any chemical species.
References
1. D. Braga, L. Maini, F. Grepioni, Chem. Soc. Rev., 2013, DOI:10.1039/C3CS60014A.
2. D. Braga, S. d’Agostino, E. Dichiarante, L. Maini, F. Grepioni, Chem. Asian J., 2011, 6 2214 – 2223.
3. D. Braga, L. Maini, F. Grepioni, Chem. Commun., 2010, 46, 6232-6242.
6-7 June 2013, Milan, Italy
28
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Porosity in flexible metal-organic systems
1
L. Barbour1
Department of Chemistry, University of Stellenbosch, Stellenbosch, South Africa
E-mail: [email protected]
Over the past decade the study of porous crystalline solids has become highly topical, especially
with regard to potentially important applications such as gas storage, separation and sensing. Wellknown systems include zeolites and metal-organic frameworks and, to a lesser extent, organic
molecular crystals. However, discrete metal complexes have received little attention as components
of porous materials. One of the basic tenets of the solid state is that molecules tend to pack closely,
thus affording minimal free space at the molecular scale. We are attempting to overcome this
tendency by designing simple complexes that cannot pack efficiently without including solvent
molecules. Indeed, we are specifically interested in forming solvent-templated complexes that do
not collapse upon subsequent solvent removal [1-6]. We have recently discovered several systems
that behave in this manner; some of these structures can be considered to be porous in the
conventional sense, but we have also noted that conventional porosity is not a prerequisite for mass
transport in the solid state. These systems have now been studied using a variety of complementary
techniques, including X-ray diffraction, isothermal gas sorption, calorimetry and molecular
modeling. Non-conventional use of these techniques has enabled us to gain a deep understanding of
the relationship between structure and gas sorption dynamics.
Figure 1: Generation of solvent-templated channels.
References
1. L. DobrzaĔska, G. Lloyd, H.G. Raubenheimer, L.J. Barbour, J. Am. Chem. Soc. 2006, 128, 698.
2. L. DobrzaĔska, G. Lloyd, C. Esterhuysen, L.J. Barbour, Angew. Chem. Int. Ed. 2006, 45, 5856.
3. S. Potts, L.J. Barbour, D. Haynes, J. Rawson, G.O. Lloyd, J. Am. Chem. Soc. 2011, 133, 12948.
4. T. Jacobs, G. Lloyd, J.-A. Gertenbach, K.K. Müller-Nedebock, C. Esterhuysen, L.J. Barbour, Angew.
Chem. Int. Ed. 2012, 51, 4913.
5. M. Lusi, L.J. Barbour, Angew. Chem. Int. Ed. 2012, 51, 3928.
6. I. Grobler, V.J. Smith, P.M. Bhatt, S.A. Herbert, L.J. Barbour, J. Am. Chem. Soc. 2013, 135, 6411.
6-7 June 2013, Milan, Italy
29
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
6-7 June 2013, Milan, Italy
30
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
SESSION V
Chairman: Mike Zaworotko
6-7 June 2013, Milan, Italy
31
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Self-assemblies for Biomimetic Materials
1
O. Ikkala1
Department of Applied Physics, Aalto University (formerly Helsinki University of Technology),
Espoo, Finland
E-mail: [email protected]
Biological materials characteristically involve self-assembled structures at different length scales
using subtle combinations of supramolecular interactions of various strengths. Inspired by them, we
have pursued towards hierarchical self-assemblies for novel functions by using simpler tectons,
allowing rational constructs. Among the most straightforward approaches for hierarchies is to use
structural units of different sizes, ranging from low molecular weights to polymers and to colloids,
connected by physical interactions, such as hydrogen bonds, coordinations, ionic bonds, and even
halogen bonds. This talk reviews various approaches. Combining polymeric and low molecular
weight supramolecular adducts of block copolymers and low molecular weight units leads to a wide
variety of hierarchies.1 Selecting polypeptidic blocks therein allows to additionally control the
secondary structure to be D-helical, E-sheet, and random coil within the self-assemblies.2-6 On the
other hand, combining colloidal level units, such as nanoclay sheets or nanocellulose nanofibers
with polymers leads to biomimetic nanocomposites with feasible mechanical properties.7-10 Finally
one can combine colloidal, polymeric, and low molecular weight units in supramolecular constructs
leading to biomimetic structures, providing sacrificial bonds for promoted toughness.11
References
1. O. Ikkala, G. ten Brinke, Science, 2002, 295, 2407-2409.
2. S. Junnila, N. Houbenov, A. Karatzas, N. Hadjichristidis, A. Hirao, H. Iatrou, O. Ikkala, Macromolecules,
2012, 45, 2850-2856.
3. S. Junnila, N. Houbenov, S. Hanski, H. Iatrou, N. Hadjichristidis, O. Ikkala, Macromolecules, 2010, 43,
9071-9076.
4. J. Haataja, N. Houbenov, H. Iatrou, N. Hadjichristidis, A. Karatzas, C. F. Faul, P. Rannou, O. Ikkala,
Biomacromolecules, 2012, 13, 3572-3580.
5. N. Houbenov, J. S. Haataja, H. Iatrou, N. Hadjichristidis, J. Ruokolainen, C. F. J. Faul, O. Ikkala, Angew.
Chem., Int. Ed., 2011, 50, 2516–2520.
6. S. Hanski, S. Junnila, A. J. Soininen, J. Ruokolainen, O. Ikkala, Biomacromolecules, 2010, 11, 34403447.
7. A. Walther, I. Bjurhager, J.-M. Malho, J. Ruokolainen, J. Pere, L. A. Berglund, O. Ikkala, Nano Letters,
2010, 10, 2742–2748.
8. M. Wang, A. Olszewska, A. Walther, J.-M. Malho, F. H. Schacher, J. Ruokolainen, M. Ankerfors, J.
Laine, L. A. Berglund, M. Österberg, O. Ikkala, Biomacromolecules, 2011, 12, 2074-2081.
9. H. Rosilo, E. Kontturi, J. Seitsonen, E. Kolehmainen, O. Ikkala, Biomacromolecules, 2013, in press.
10. J. R. McKee, E. A. Appel, J. Seitsonen, E. Kontturi, O. A. Scherman, O. Ikkala, 2013, submitted.
11. L. Martikainen, A. Walther, J. Seitsonen, L. A. Berglund, O. Ikkala, 2013, submitted.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Porous Coordination Networks: Structures, Entanglements and Properties
L. Carlucci, G. Ciani, D. M. Proserpio
Dipartimento di Chimica, Università degli Studi di Milano, Via C. Golgi 19, Milano, 20133, Italy
E-mail: [email protected]
The great current interest for Coordination Networks (CNs) and Metal-Organic-Frameworks
(MOFs) as new functional solid materials is, nowadays, well evidenced by the exponential growth
of the number of related research papers. Important fields of application for these materials are the
storage and separation of gases, catalysis, ion exchange, molecular sensing, optics, magnetism and
others.
These extended coordination compounds are highly crystalline and crystallography has a
fundamental role in their characterization and rapid development. Their complex networked
structures, as well as their possible entanglements in the solid state (e.g. interpenetration and
polycatenation), can be elucidated in details through structural and topological analyses. The
synthesis by design of structures with controlled properties also takes great advantage from
crystallographic and topological information.
We are involved in the field and are particularly interested to entangled species. In this contribution
our approach to the synthesis and characterization of porous coordination networks will be
illustrated and discussed through selected examples. These comprise entangled flexible porous
species [1], obtained by one-step self-assembly processes, and hetero-metallic open networks
assembled by a stepwise approach [2].
Figure 1: On the left a schematic view of the polycatenation in [Cu5(bpp)8(SO4)4(EtOH)(H2O)5](SO4).Solv [bpp= 1,3Bis(4-pyridyl)propane]; on the right a CPK view of the monodimensional channels in [ZnL3Ag3](ClO4)2·Solv [L= 1,3Bis(4’-cyanophenyl)-1,3-propanedionato
References
1. L. Carlucci, G. Ciani, M. Moret, D. M. Proserpio, S. Rizzato, Angew. Chem. Int. Ed. Engl., 2000, 39,
1506-1510
2. L. Carlucci, G. Ciani, S. Maggini, D. M. Proserpio, M. Visconti, Chemistry-a European Journal, 2010,
16, 12328-12341.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Recognition And Sensing with Polyamine-based Hosts: Structural Aspects
1
P. Paoli1
Dipartimento Ingegneria Industriale,University of Firenze, Italy
E-mail: [email protected]
The discovery of novel, more effective and more selective synthetic host molecules continues to be
a challenging task in host-guest chemistry.[1] Size, shape and electronic complementarity, nowdays
well established general principles on which rests the host-guest recognition event, must be taken
into account when designing host structures. In some cases the preorganization of the receptor,
given that it maximizes host-guest interactions, is also mandatory in order to get good
performances. In addition, by coupling the binding site with a “signaling subunit” capable of giving
information about the binding event, such as color changes or modification of the fluorescence
emission behavior, a chemosensor can be devised.[2]
Given that the challenge is to find the best way to maximize the strength of the desired host-guest
interactions, key steps in devising efficient hosts are: the choice of the donor atom set, which
characterizes the binding pocket; the design of the overall host architecture, which can impart
flexibility / rigidity / shape complementarity / solubility; the insertion of ad-hoc groupings to
consolidate the host-guest interactions and, if the case, to signal the binding event.
Over the years we have applied these fundamental concepts to the design of artificial receptors able
to recognize and sometime sensing charged guests, mainly in aqueous solution.[3] In this context
polyamine based receptors are proved to be quite versatile as water soluble ligands. Our most
common hosts have macrocyclic skeletons, which usually means strong affinity and selective
binding towards a wide variety of charged guests. Attention has been paid to metal-containing
receptors for selective recognition, activation and signaling of additional species.
Examples from our recent studies on such host-guest systems will be presented, focusing in
particular on the relationships between structural peculiarities and performances.
References
1. J.W. Steed, D.R. Turner, K.J. Wallace, Core Concepts in Supramolecular Chemistry and Nanochemistry ,
John Wiley & Sons, Chichester, 2007.
2. M. Formica, V. Fusi, L. Giorgi, M. Micheloni, Coord. Chem. Rev., 2012, 256, 170-192.
3. C. Benelli, E. Borgogelli, M. Formica, V. Fusi, L. Giorgi, E. Macedi, M. Micheloni, P. Paoli, P. Rossi,
Dalton Trans., 2013,42,5848-5859; S. Amatori, G. Ambrosi, M. Fanelli, M. Formica, V. Fusi, L. Giorgi,
E. Macedi, M. Micheloni, P. Paoli, R. Pontellini, P. Rossi, M. A. Varrese, Chem. Eur. J., 2012, 18, 42744284; G. Ambrosi, M. Formica, V. Fusi, L. Giorgi, E. Macedi, M. Micheloni, P. Paoli, R. Pontellini, P.
Rossi, Chem. Eur. J., 2011, 17, 1670-1682; G. Ambrosi, M. Formica, V. Fusi, L. Giorgi, E. Macedi, M.
Micheloni, P. Paoli, R. Pontellini, P. Rossi, Inorg. Chem., 2010, 49, 9940-9948.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
SESSION VI
Chairman: Pierangelo Metrangolo
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
From tectons to crystals of crystals
M. W. Hosseini
University of Strasbourg, Strasbourg, France
[email protected]
The design and construction of periodic architectures in the crystalline phase or at surfaces are
attracting considerable interest over the last two decades. For both design and analysis of molecular
crystals, we have developed a strategy called molecular tectonics which is based on the formation of
molecular networks through the design of complementary tectons or molecular construction units.
The generation of molecular networks and subsequently of crystals is achieved by self-assembly
processes based on repetitive molecular recognition events. This approach, combining
supramolecular synthesis and self-assembly processes in the solid state, is operational and versatile
and allows the design and construction of not only a variety of complex purely organic or hybrid
architectures but also of crystals of crystals. The approach will be presented and illustrated by a
variety of tectons, networks and crystals of crystals.
References
1. M. W. Hosseini, Acc. Chem. Res., 2005, 38, 313.
2. M. W. Hosseini, Chem. Commun., Focus Article, 2005 ,582.
3. M. W. Hosseini, CrytsEngComm., 2004, 6, 318.
4. P. Dechambenoit, S. Ferlay, N. Kyritsakas, M. W. Hosseini, J. Am. Chem. Soc., 2008, 130, 17106.
5. P. Dechambenoit, S. Ferlay, N. Kyritsakas, M. W. Hosseini, Chem. Commun., 2009, 1559.
6. P. Dechambenoit, S. Ferlay, N. Kyritsakas, M. W. Hosseini,Chem. Commun., 2010, 46, 868.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
At The Limits In Situ Crystallization for Structure Determination
R. Boese
University Duisburg-Essen, 45117 Essen, Germany and
Ruhr-Universität, Excellence Cluster RESOLV, 44801 Bochum, Germany
E-mail: [email protected]
Crystallization of liquids and gases in capillaries at low temperatures mounted at the X-ray
diffractometer is an old technique. Nowadays it is facilitated by software controlled heating of a
small zone in a capillary with an infrared laser, called optical heating and crystallization device
(OHCD). It allows crystallizing liquid crystals, plastic crystals, ionic liquids, disordered crystals,
compounds which form glassy states, which shatter during phase transitions, which decompose
without mother liquor or must be kept at pressures up to 100 bar in quartz capillaries.
A dozen of selected highlights from our group which simultaneously represent the most
extreme experimental challenges are reviewed here. They demonstrate the immense possibilities for
achieving new insights in classical fields of chemistry, but also in material
sciences, supramolecular chemistry paired with computational chemistry.
x Propane has the lowest melting point of all organic compounds;
crystallized and measured at 40 K revealed its properties caused by the
unfavorable packing with much space between the molecules.1 (fig.right)
x Cyclopropane and derivatives are the most strained organic molecules.
Spiro-compounds and rotanes are thermosensitive and their geometry
was heavily discussed in the context of quantum chemical calculations.2
(no fig.)
x Cyclopropabenzene was considered as one of the test cases of bond
localization in aromatic systems. It has strongly ‘bent bonds’ revealed by
BCPs. For unknown reasons this low-melting compound has an extreme
odor, even penetrating through a sealed capillary.3 (fig. right)
x Norbornadiene forms plastic crystals on cooling, like norbornane, norbornadiene and other
globular molecules. Ordered crystals can be achieved by in situ crystallization from a lowmelting organic solvent below the glass transition.4 (no fig.)
x C60 is disordered at ambient; we unsuccessfully tried to achieve non-disordered crystals by
sublimation at 90K into the tip of an evacuated quartz capillary. Carbon makes quartz fragile
which caused the capillaries to break, but in principal the method should
work. (no fig.)
x Methane Hydrates have a paramount importance in economy, ecology and
sciences. Single crystal structures could be determined by extreme slow
crystallization in pressurized capillaries (ca. 50 bar). Many tiny crystals
diffracting simultaneously and merged data established the so-called 'oligocrystallography' as an intermediate between powder and single crystal
crystallography.5 (fig. right)
x Acetylene-Benzene Cocrystal is the prototype of -CH...ʌ interactions. It
probably represents the most abundant cocrystal in the Universe because it
is suspected to exist as 300 m high dunes at the shores of the oceans
(Ontaria Lacus) of hydrocarbons at Saturn's moon Titan. (fig. right)
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
The Cassini spacecraft mission started in 1997 and the Huygens probe
landed there in 2005 providing some evidence for this assumption.6
x Chlorinefluoride is the smallest interhalogen compound; surprisingly,
the crystal packing does not follow the dipoles instead Type2
interactions with the shortest intermolecular Cl···Cl distance (3.070Å)
whereas the F···F distances are normal (2.92Å). An extremely low
melting point (-156 °C) and the aggressive gas reacting with almost
everything, organics, glass and most metals called for the most difficult
experiment.7 (fig. right)
x Ammonia-Acetylene cocrystals represent the archetype of cocrystals
consisting of the smallest hydrogen bond acceptor and donor molecules.
They form zigzag chains where ammonia nitrogen accepts the hydrogen
atoms of two acetylene molecules.8 (fig. right)
x 3-Ethynylcyclopropene decomposes above -100 °C which requires
condensing into an evacuated capillary directly from the reaction column
representing a most delicate procedure. The double bond in the ring is the
shortest, ever experimentally determined by X-ray diffraction.9 (fig. right)
x D5-Pyridine has a different crystal structures for the perdeuterated and the protonated form
which represents the rare case of so-called isotopic
polymorphism. Perdeuterated pyridine was crystallized from a
solution of n-pentane at low temperatures with one independent
molecule in the asymmetric unit. In contrast, protonated
pyridine does not exist in this low temperature form and
crystallizes with four molecules in the asymmetric unit only.
Further similar cases have been published recently.10 (fig. right)
x D-Ribose is a highly flexible molecule which is why it is
difficult to crystallize and why the crystal structure of this
important molecule was unknown until recently. Crystallization
at low temperature from solution was the adequate successful technique.11 (no fig.)
References
1. V. R. Thalladi, R. Boese, New J. Chem., 2000, 24, 579.
2. a) R. Boese, D. Bläser, K. Gomann, U. H. Brinker, J. Am. Chem. Soc. 1989, 111, 1501. b) R. Boese, T.
Miebach, A. de Meijere, J. Am. Chem. Soc., 1991, 113, 1743. c) A. de Meijere, S. Kozhushkov, C. Puls,
Th. Haumann, R. Boese, M. J. Cooney, L. T. Scott, Angew. Chem. Int. Ed. Engl., 1994, 33, 869.
3. R. Neidlein, D. Christen, V. Poignée. R. Boese, D. Bläser, A. Gieren, C. Ruiz-Pérez, T. Hübner, Angew.
Chem. Int. Ed. Engl., 1988, 27, 294.
4. J. Benet-Buchholz, T. Haumann, R. Boese, Chem Comm., 1998, 2003.
5. M.T. Kirchner, R. Boese, W.E. Billups, L.R. Norman J. Am. Chem. Soc., 2004, 126, 9407.
6. a) R. Boese, T. Clark, A. Gavezzotti, Hel. Chim. Act., 2003, 86, 1085; b) R.N. Clark et al., J. Geophys.
Res., 2010, 115, 2156.
7. R. Boese, A. D. Boese, D. Bläser, M. Yu. Antipin, A. Ellern, K. Seppelt, Angew. Chem. Int. Ed. Engl.,
1997, 36, 1489.
8. R. Boese, D. Bläser, G. Jansen, J. Am. Chem. Soc., 2009, 131, 2104.
9. K. K. Baldridge, B. Biggs, D. Bläser, R. Boese, M. M. Haley, A. H. Maulitz, J. S. Siegel, Chem. Comm.,
1998, 1137.
10. S. a) Crawford, M.T. Kirchner, D. Bläser, R. Boese, W.I.F. David, A. Dawson, A. Gehrke, R.M.
Ibberson, W.G.Marshall, S. Parsons and O. Yamamuro, Angew. Chem., 2009, 121, 769. b) O.V. Shishkin,
S.V. Shishkina, A.V. Maleev, R.I. Zubatyuk, V. Vasylyeva, K. Merz, ChemPhysChem., 2013, 14, 847.
11. D. Sisak, L. B. McCusker, G. Zandomeneghi, B. H. Meier, D. Bläser, R. Boese, W. B. Schweizer, R.
Gilmour, J. D. Dunitz, Angew. Chem., 2010, 122, 4605.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
In situ cryocrystallization of halogen bonded supramolecular complexes
1
G. Terraneo,1 G. Cavallo,1 T. Pilati,1 P. Metrangolo,1 G. Resnati, 1
NFMLab, Department of Chemistry, Materials and Chemical Engineering ”G. Natta”, Politecnico
di Milano, via Mancinelli 7, 20131 Milano, Italy
E-mail: [email protected]
The in situ cryocrystallization technique offers a unique opportunity for the structural study of low
melting materials. Boese [1] and others [2] have proven the potential of the technique in the study
of weak and elusive interactions (e.g. CH…S hydrogen bonds, halogen…halogen contacts, etc.) in
supramolecular structures, polymorphs, functional materials, etc.
Halogen bond (XB) has consolidated its role of reliable tool in crystal engineering involving
perfluorinated systems [3]. Strong XBs have been the object of extensive crystallographic studies
and detailed information are available on the structural profile of these interactions. Weaker XBs
have received much less attention, as they give rise to less reliable supramolecular synthons and it is
more likely that weak and ubiquitous interactions frustrate the crystal packing design. Numerous
structures in the Cambridge Structural Database prove that C-XÂÂÂO interactions (X = Br or Cl),
typical weak XBs, are able to influence the crystalline packing. However details on structural
features and role of the C-XÂÂÂO supramolecular synthon can be hardly surmised from these
structures as nearly all of them were obtained serendipitously and/or involve quite complex and
random molecules.
In this communication we report a structural study using in situ cryocrystallization technique of
dihaloperfluorocarbons and their halogen bonded adducts (Figure 1) formed with systems having an
oxygen atom as halogen bonding acceptor [4]. These tectons have been chosen to maximize the
possibility that the crystal structure gives reliable indications on the XÂÂÂO synthon and its role in
driving the self-assembly process.
Figure 1: Crystal packing of cocrystal composed by 1,2-dibromotetrafluoroethane and HMPA
References
1. M. T. Kirchner, D. Blaser, R. Boese, Chem.–Eur. J. 2010, 16, 2131- 2146.
2. G. Dikundwar, R. Sathishkumar, T. N. Guru Row, G. R. Desiraju, Cryst. Growth Des. 2011, 11, 39543963; D. S. Yufit, J.A.K. Howard, CrystEngComm. 2010, 12, 737-741.
3. P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, Angew. Chem., Int. Ed. 2008, 47, 6114-6127.
4. S. K. Nayak, G. Terraneo, A. Forni, P. Metrangolo, G. Resnati, CrystEngComm 2012, 14, 4259-4261.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
Fluorine and Deuterium: Influence on the crystal architecture.
1
V. Vasylyeva1, Klaus Merz,2 Oleg V. Shishkin3
Department of Inorganic and Structural Chemistry, Heinrich Heine University Duesseldorf,
Duesseldorf, Germany
2
Inorganic Chemistry I Department, Ruhr-University Bochum, Bochum, Germany
3
Institute for Single Crystals, National Academy of Science of Ukraine, Kharkiv, Ukraine
E-mail: [email protected]
While the character of classical strong intermolecular interactions is largely understood, the
influence of weak intermolecular interactions on the self-organisation of molecules in the solid state
raises many questions. Continuing our investigations on aggregation of substituted aromatic
molecules,[1-2] we studied the influence and boundaries of weak directing substituents deuterium
and fluorine on the aggregation of small molecules.
Hydrogen/deuterium-exchange, the smallest possible modification of a molecule, is generally seen
as a non-dominating parameter in the formation of crystal structures. On the other hand, we can
show that the aggregation of molecules in the solid state of polymorphic N-heterocyclic systems
like pyridine N-oxide or acridine can be very sensitive on small changes of the isotopic substitution
pattern of the well selected molecules.[3,4]
The question about the role of fluorine in intermolecular interactions is discussed controversially.
We investigated a range of partially fluorinated pyridines and analysed their crystal packing
experimentally and theoretically. In situ cryo-crystallisation, a powerful technique to control the
crystal growth, was used to investigate crystal structures of low melting fluorinated pyridines
followed by geometrical analysis of the crystal packing based on the on the orientation of the
molecules with respect to each other as well as on the presence of short intermolecular contacts. To
deepen the understanding of the processes leading to a crystal formation theoretical study of the
energies of weak intermolecular interactions using the MP2/6-311 G(d, p) level of theory - is an
innovative method for research of the basic motives in the solid state - were performed. The
comparison of our experimental and theoretical findings shows the interplay of halogen and
hydrogen bonding, in particular how fluorine atoms influence the aggregation of substituted
pyridines. [5]
References
1. V. Vasylyeva, K. Merz, J. Fluorine Chem. 2010, 131, 446-449.
2. V. Vasylyeva, K. Merz, Cryst. Growth Des. 2010, 10, 4250-4255.
3. V. Vasylyeva, T. Kedziorski, N. Metzler-Nolte, C. Schauerte, K. Merz, Cryst. Growth Des. 2010, 10,
4224-4226.
4. A. Kupka, V. Vasylyeva, D. W. M. Hoffmann, K. V. Yusenko, K. Merz, Cryst. Growth Des. 2012, 12,
5966-5971.
5. V. Vasylyeva, O. V. Shishkin, A. V. Maleev and K. Merz, Cryst. Growth Des. 2012, 12, 1032-1039.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
POSTERS
6-7 June 2013, Milan, Italy
41
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P1
Supramolecular Interactions as Glue for the design of Smart Architectures
1
I. Bassanetti1, A. Comotti1, S. Bracco1, L. Marchio2, P. Sozzani1
University of Milano Bicocca,Department of Materials Science, Via R. Cozzi 53, Milano, Italy
2
University of Parma, Department of Chemistry, Parco Area delle Scienze 17/a, Parma,
Italy
E-mail: [email protected]
Weak interactions such as ʌ-ʌ, CH-ʌ, H bonds and VdW forces, play a key role in the rational
design of new fascinating supramolecular materials. In effect these interactions are able to drive the
self-assembly of simple building blocks to create well defined molecular polyhedra. These materials
have attracted much attention not only for their infinite range of application but also thanks to their
very interesting supramolecular architectures. Here we present how 72 H-bonds guide the assembly
of two kinds of hexagonal molecular tiles in a quasi-truncated octahedron q-TO (which corresponds
to one of the 13 Archimedean solids)1 and how different counterions (BF4-, PF6- or NO3-, CF3SO3-)
can largely modulate the structure of hexameric toroidal supramolecules h-SP which, at higher
hierarchical level, can assembly in sphere2. Both q-TO and h-SP crystallize in high symmetric cubic
space groups and both present a void volume inside the macrostructure: q-TO have a 2200Å3 of
free total volume and it exhibits the remarkably ability of encapsulate a large assortment of
molecular species as solvent molecules and organic guests; h-SP shows a permanent porosity with
18000 Å3 of void space and it is a good material for the adsorption of gases such as CO2 or solvent
vapors. Porous dipeptide-based crystals held together by hydrogen bonds and showing selective
adsorption of CO2 vs N2 are also presented.3
Figure 1: From the left: Scanning Electron Microscope image of a crystal of compound q-TO and a picture of a crystal
of h-SP
References
1. Y. Liu, C. Hu, A. Comotti, M.D. Ward, Science, 2011, 333, 436-440.
2. I. Bassanetti, F. Mezzadri, A. Comotti, P. Sozzani, L.Marchiò, JACS, 2012, 134, 9142-9145.
3. A. Comotti, A. Fraccarollo, S. Bracco, M. Beretta, P. Sozzani, CrystEngComm, 2013, 15, 1503-1507.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P2
Porous Dipeptide Crystals and Organic Frameworks as Polymerization Vessels
1
M.Beretta1, A. Comotti1, S. Bracco1, P. Sozzani1
University of Milano Bicocca, Department of Materials Science, Via R. Cozzi 53, 20125 Milan,
Italy.
E-mail: [email protected]
Our work was aimed at performing polymerizations in porous materials and controlling solid state
reactions of the new adducts with polymers. The project exploits the unprecedented potentials of
porous materials presently in use, which range from fully-organic covalent frameworks and metalorganic frameworks to porous molecular crystals of biological origin, while the properties induced
to the polymers include stereochemistry, chain alignment and morphology.
The extraordinary surface areas (> 5000 m2/g) and pore capacity exhibited by porous aromatic
frameworks (PAFs) interconnected by covalent bonds, allow sorption of a large amount of
monomers to form high-molecular-mass polymers tightly interwoven with the porous matrix [1].
Polyacrylonitrile (PAN) obtained by this way could undergo in-situ thermal transformation to
conductive, semi-conductive polymers and carbon nano-fibers. PAN was also synthesized in the
form of isotactic polymer within the nanochannels of dipeptide crystals which were used as
sacrificial polymerization vessels [2]. The crystalline matrix sublimed away over 250 °C after a
polymer intramolecular reaction to yield a rigid 'ladder' polymer, which retained the morphology of
the crystal scaffold. In a third example, the metal-organic host framework can participate with two
reactive vinyl pendant groups in the polymerization, resulting in a cross-linked network [3]. The
crystal scaffold of the host was removed except at cross-linking points, which act as clipping points
for the aligned polymer chains. Although the polymer chains are atactic, they are kept in register by
the molecular clips and chain-periodicity was ascertained by XRD and TEM.
An intriguing aspect of porous crystalline frameworks is the dynamics of molecular elements in the
pore-walls. Since these mobile elements behave as rotors and are exposed collectively to the
structural voids in the porous material, their motion could be switched on and off by intervening
molecular species migrating into the crystal channels. The fast rotor dynamics was hampered by
guests occupying the crystal voids and released after absorbate removal. This effect was realized in
mesoporous hybrid materials and porous molecular crystals.
References
1. A. Comotti, S. Bracco, M. Mauri, S. Mottadelli, T. Ben, S. Qiu, P. Sozzani, Angew. Chem. Int Ed. 2012,
51, 10136-10140.
2. G. Distefano, A. Comotti, S. Bracco, M. Beretta, P. Sozzani, Angew. Chem. Int Ed. 2012, 51, 9258-9262.
3. G. Distefano, H. Suzuki, M. Tsujimoto, S. Isoda, S. Bracco, A. Comotti, P. Sozzani, T. Uemura, S.
Kitagawa, Nature Chem. 2013, 5, 335-341.
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P3
New Hybrid Organic-Organometallic Nano-ribbons
R.Bertani1, P.Sgarbossa1, V. Di Noto2, M. Piga2, G. Giffin2, G.Terraneo3, T.Pilati3, P.Metrangolo3,
G.Resnati3
1
Department of Industrial Engineering, UNIPD, via F. Marzolo, 9 , I- 35132 Padova (Italy);
2
Department of Chemical Sciences, UNIPD, via F. Marzolo, 1 , I- 35132 Padova (Italy)
3
NFMLab, Department of Chemistry, Materials and Chemical Engineering, POLIMI, via
Mancinelli 7, I-20131 Milano
[email protected]
New Hybrid Organic-Organometallic crystal Nano-Ribbons for use as low-k gate dielectric
materials in micro-/ nano-electronic devices such as OTFTs have been prepared by cocrystallization of trans-[PtL2(CŁC-4-py)2] with 1,4-diiodoperfluorobenzene, (E)-4,4’-diiodo2,2’,3,3’-octafluorostilbene, and 1,2-diiodotetrafluoroethane.1,2 Strong NÂÂÂI-C halogen-bond drives
the self-assembly resulting in the co-crystal formation. The co-crystals have been obtained by
isothermal evaporation at room temperature of a chloroform solution containing the trans[Pt(CŁCPy)2(PCy3)2] and the corresponding fluorinated derivative. X-ray structure determinations
show that other non-covalent interactions help the construction of the crystal packing.
Figure 1: Crystal packing of the adduct trans-
Figure 2: Crystal packing of the adduct trans-
[PtCl2(PEt3)2(CԘC-4-py)2]+I2C6F4
[PtCl2(PCyt3)2(CԘC-4-py)2]+I2C2F4
The structural and dielectric properties are discussed in terms of ancillary ligands in platinum
coordination sphere and perfluoroalkyl- or aryl-iodide derivative. The wide variety of crystal
architectures based on MLn complexes where ancillary ligands (i.e. phosphines) and moieties
suitable for non-covalent interactions involving electron deficient halogens can be inserted, opens
new perspectives for using organometallic systems in the achievement of functional materials with
tunable properties for advanced applications.
References
1. P.Sgarbossa, R.Bertani, V. Di Noto, M. Piga, G. Giffin, G.Terraneo, T.Pilati, P.Metrangolo, G.Resnati,
Cryst. Growth Des. 2012, 12, 297-305.
2. R.Bertani, P.Sgarbossa, V. Di Noto, M. Piga, G.Terraneo, T.Pilati, P.Metrangolo, G.Resnati, manuscript
in preparation
3. R. Bertani, P. Sgarbossa, A. Venzo, F. Lely, M. Amati, G. Resnati, T. Pilati, P. Metrangolo, G. Terraneo,
Coord. Chem. Rev., 2010, 254, 677-695.
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P4
Synthesis Of A Coumarin - NBD Calix[4]arene System And Spectroscopic Study
Of Its Energy Transfer Properties
I. Tosi1, L. Baldini1, S. Bertella1, F. Sansone1, F. Terenziani1.
1
Dipartimento di Chimica, Università degli Studi di Parma, Parco Area delle Scienze 17A, 43124
Parma, Italy.
E-mail: [email protected]
This research work is focused on the synthesis of new small molecules which could be used as
active layer in Organic Solar Cells (OSCs) thanks to their ability to perform energy and charge
transfer.
According to Förster’s theory, efficient energy transfer within a multichromophoric system can be
achieved when the following requirements are met:
x Distance between the donor and acceptor chromophores less than 10Å;
x Only weak (electrostatic) interactions between the chromophores;
x Overlap between the absorption spectrum of the acceptor and the fluorescence spectrum of
the donor.
We therefore chose Coumarin 343 as donor and NBD as acceptor, while to maintain these two units
at the correct distance we selected the calix[4]arene scaffold.
In this communication we report the synthesis of bichromophoric compound 1 and the
spectroscopic studies of the energy transfer between the chromophores.
The spectroscopic analysis conducted in CHCl3 demonstrates an efficient radiationless energy
transfer from Coumarine 343 to NBD. This transfer was confirmed by the decrease of the
fluorescence intensity of the donor and by the enhancement of the acceptor fluorescence in
compound 1 with respect to the isolated chromophores.
Unfortunately we couldn’t quantify the transfer efficiency according to the Förster theory because
of the presence of strong interactions between the two chromophores in CHCl3.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P5
X-Ray Diffraction is the experimental arm of Crystallography.
Known and unknown tribute of Pisa from last towards next twenties
G. Berti1,2, F. De Marco2, S. Aldrighetti2,3
1,
University of Pisa, Pisa, Italy
2
XRD-Tools s.r.l, Pisa, Italy
3
OET – Ponte Arche (Tn), Italy
E-mail: [email protected]
Nello Carrara, Franco Rasetti and Enrico Fermi, still under graduated students in those twenties of
past century were essaying themselves in the initial steps in their Science adventure. Their
supervisor Prof. Luigi Puccianti, realized quite soon the intellectual quality of those three boys and
leave them to work around freely in the laboratory of Physics. E. Fermi, the youngest among them
become quickly the group leader and addressed the friend’s interest towards the Röngten rays, still
relatively unknown subject, but more and more important and increasing in popularity. In his thesis
of degree in Physics Fermi deals with x-ray diffraction introducing a certain criticism on the Debye
approach, even if the Netherlander scientist had already advanced achievements. It is of interest
here to focus on the experimental aspects that are the less known among the Fermi paramount
contribution to Science. The young group of Pisa should have met some difficulties to obtain clean
images on the [BaPt(CN)4] screen from either plane and curved foils of micas. The Fermi’s intuition
was attracted by the low efficiency of the vacuum Röngten tube; the glass absorption edge is in fact
compatible of the emission energy of the Fe anode he used for such
experiments. The boys decided to design a different x-ray source with
using a dynamic vacuum. Prof. Puccianti agreed to by a very expensive
Gaede-Cacciai mercury rotary pump and the technical laboratory of
Physics manufactured the x.ray glass tube with windows and the
appropriate joints and adapters between tube and pumps.[1]
With high respectful to so bright past we are happy to see that Pisa still
continue his vocation on experimental x-ray diffraction by proposing
for next twenties new concept for “on site XRD” with a certain
confidence of success coming from most recent achievements and
prototypes.
Figure 1: New prototype of DifRob®, a dffractometer for the application
of X-ray diffraction on site as not destructive testing method.[2].
Acknowledgment
Prof. Roberto Vergara Caffarelli for kind availability to discuss on the Activity of Enrico Fermi.
1. R. Vergara Caffarelli, “Enrico Fermi, Immagini e documenti”, Ed. Plus 2001 Pisa
2. G. Berti “Diffractometer and Method for diffraction analysis” EP 1470413 April 7th, 2010.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P6
The Effect of the Fluorine Substitution on Supramolecular Assemblies of Aryl
Benzyl Sulfoxides
1
C. Cardellicchio1, M. A. M. Capozzi2, F. Capitelli3
CNR ICCOM, Dipartimento di Chimica, via Orabona 4, Bari, Italy.
2
Dipartimento di Chimica, via Orabona 4, Bari, Italy.
3
CNR IC, via Salaria, Km 29.300, Monterotondo (Rome), Italy.
E-mail: [email protected]
Our recent work on the enantioselective synthesis of sulfinyl compounds [1-2] has yielded a
collection of enantiopure sulfoxides, whose crystal structures has been investigated by X-ray
diffraction analysis. Among the investigated compounds, enantiopure aryl benzyl sulfoxides show a
common supramolecular motif, consisting in a CH···O interaction between one of the methylene
hydrogen atom of the benzyl moiety and the sulfinyl oxygen atom [1-2].
On the other hand, different interesting supramolecular assemblies were observed when a single
fluorine atom or a whole pentafluorophenyl moiety [3] are present in the molecules.
Among the others, we recognized both parallel displaced stacking plots of similar aryl groups and
parallel displaced head-to-tail stacking plots between pentafluophenyl and phenyl groups (Figure 1),
two supramolecular assemblies reported in fluoroorganic chemistry [3]. In the last case, we
observed also a T-shape arrangement of the aryl groups belonging to different chains of stacking
planes.
The complete list of supramolecular motifs found in these molecules will be described.
Figure 1: Stacking plot of aryl groups in (R)-benzyl pentafluorophenyl sulfoxide
References
1. F. Naso, M.A.M. Capozzi, A. Bottoni, M. Calvaresi, V. Bertolasi, F. Capitelli, C. Cardellicchio, Chem.
Eur. J. 2009, 15, 13417-13426 and references therein.
2. M.A.M. Capozzi, F. Capitelli, A. Bottoni, M. Calvaresi, C. Cardellicchio, ChemCatChem 2013, 5, 210219.
3. R. Berger, G. Resnati, P. Metrangolo, E. Weber, J. Hulliger, Chem. Soc Rev. 2011, 40, 3496-3508.
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P7
Activation of room temperature phosphorescence of organic co-crystals.
A novel approach based on Halogen-Bond.
L. Catalano1, A. Bertocco1, S. D'Agostino1, B. Ventura2, F. Grepioni1, D. Braga1.
1
Dipartimento di Chimica G. Ciamician, Università di Bologna, via Selmi 2, Bologna, Italy
2
Istituto ISOF-CNR, via P. Gobetti 101, Bologna, Italy
E-mail: [email protected]
There are only few works concerning room temperature phosphorescence of metal-free organic
crystals.[1,2] This is essentially due to the spin forbiddenness of the intersystem crossing process
and to structural and energetic constraints typical of solid state. In order to obtain phosphorescence
from purely organic compounds,1-8 Naphthalenimides are good candidates for, at least, two
reasons: in aromatic carbonyls the triplet state generation is efficient and this kind of imides are
easy-to-synthesize cheap building-blocks for co-crystals.[3] In this study halogens are not used only
as a “glue”, but also they play the role of heavy-atoms to induce spin-orbit coupling in the aromatic
compounds. This effect allows the control of optical properties. The final target of the work is the
achievement of a high-quantum-yield phosphorescence at room temperature. The experimental
work is separated in two main parts. The first one is the synthesis both in conventional (solution)
and unconventional methods, such as: kneading or liquid assisted grinding (LAG), neat grinding,
ball milling; and solid state characterization (single crystal and powder x-ray diffraction,
thermogravimetric analysis and differential scanning calorimetry) of the building blocks and cocrystals. The second one is the photo-physical characterization (absorption, reflectance,
fluorescence, phosphorescence, emission at low temperature, time-correlated single photon
counting) in solution and solid state of the products.
References
1. O. Bolton, K. Lee, H.-J. Kim, K. Y. Lin, J. Kim, Nat. Chem, 2011, 3, 205-210.
2. X. Pang, H. Wang, X. R. Zhao, W. J. Jin, CrystEngComm, 2013, 15, 2722-2730.
3. S. V. Bhosale, C. H. Jani, S. J. Langford, Chem. Soc. Rev., 2008, 37, 331-342.
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P8
Fluorinated Metal-Organic Frameworks Self-Assembled via Halogen Bond
L. Colombo1,2, P. Metrangolo1,2, T. Pilati1, G. Resnati1,2, G.Terraneo1,2
1
NFMLab, D.C.M.I.C. “Giulio Natta”, Politecnico di Milano, Via L. Mancinelli 7, 20131, Milan,
Italy.
2
Italian Institute of Technology, Center for Nano Science and Technology (CNST-IIT@PoliMi),Via
Pascoli 70/3, 20133, Milan, Italy
E-mail: [email protected]
Metal-Organic Frameworks (MOFs) are crystalline materials composed of organic ligands and
metal cations with applications in areas as gas storage and separation or catalysis [1]. Recently, the
useful properties of fluorinated molecules prompted the preparation of MOFs containing fluorinated
ligands (F-MOFs). Enhanced thermal and chemical stability, high hydrophobicity of the pores and
low surface energy are expected. Only a few F-MOFs structures have been reported to date, mainly
related to gas absorption, especially H2 [2].
Tuning the properties of the network via structural control is one of the main challenges in the
MOFs field. Coordination bonds (CBs) are the main driving force in MOFs self-assembly, but other
supramolecular interactions play a significant role. The strong electronwithdrawing effect of
fluorine makes iodinated perfluorinated molecules ideal for the formation of strong XBs and we
decided to pursue the synergy of XB and CB in the self-assembly of F-MOFs.
Here we report a new Cu(II)-F-MOF containing unsaturated metal centres showing selective and
reversible solvent absorption accompanied by solvatochromic effect. The framework has been
realized employing the new ligand rac-4,4'-[1,2-bis(2,3,5,6-tetrafluoro-4-iodophenoxy) ethane-1,2diyl]dipyridine (1) specifically designed to be involved in XBs, HBs and CBs.[3]
Figure 1 – Asymmetric unit of the Cu(II)-F-MOF after MeOH absorption. Structure solved from XRPD data.
References
1. (a) J-R. Li, R.J. Kuppler, H-C. Zhou, Chem. Soc. Rev. 2009, 38, 1477-1504. (b) J.G. Lee, O.K. Fahra, J.
Roberts, K.A. Scheidt, S.T. Nguyen, J.T. Hupp, Chem. Soc. Rev. 2009, 38, 1450-1459.
2. (a) C. Yang, X. Wang, M.A. Omary, J. Am. Chem. Soc. 2007, 129, 15454-14455. (b) Z. Hulvey, E.H.L.
Falcao, J. Eckert, A.K. Cheetham, J. Mater. Chem. 2009, 19, 4307-4309.
3. (a) R. Bertani, P. Sgarbossa, A. Venzo, F. Lelj, M. Amati, G. Resnati, T. Pilati, P. Metrangolo, G.
Terraneo, Coord. Chem. Rev. 2010, 254, 677-695. (b) J. Martì-Rujas, L. Colombo, J. Lü, A. Dey, G.
Terraneo, P. Metrangolo, T. Pilati, G. Resnati, Chem. Commun. 2012, 48, 8207-8209.
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P9
Crystal Structure and Optical Properties
of Fluorinated Push-Pull J-Aggregates
V. Dichiarante1, E. Cariati2, G. Cavallo1, A. Forni3, P. Metrangolo1,
T. Pilati1, G. Resnati1, G. Terraneo1
1
NFMLab, DCMIC "G. Natta", Politecnico di Milano, via Mancinelli 7, I-20131 Milan, Italy
2
DCIMA-INSTM, Università degli Studi di Milano, via Venezian 21, I-20133 Milan, Italy
3
ISTM-CNR, Università degli Studi di Milano, via Golgi 19, I-20133 Milan, Italy
E-mail: [email protected]
J-aggregates are strongly emissive S-conjugated molecular systems arranged in head-to-tail
orientations, where electronic excitation is delocalized over several molecular units, as a result of
the significant overlap between neighboring molecules. They represent ideal candidates for
optoelectronic devices, since they combine high luminescence and good charge-conducting
properties.1
Herein we report a new push-pull system,2 based on a N,N-dimethylamino group as electron-donor
moiety and a 2,3,5,6-tetrafluorophenyl ring as electron-acceptor, connected through a p-phenylene
vinylene (PPV) spacer. Single crystal X-ray diffraction confirmed the presence of a S-Santiparallel
overlapping of tetrafluorophenyl-styryl groups, giving rise to J-aggregates with optimized arylperfluoroaryl face-to-face interactions (Fig. 1).
Figure 1: Crystal packing of the fluorinated push-pull system (Me2N-C6H4)-PPV-(C6HF4).
In order to characterize the linear and nonlinear optical behavior of such molecular system, secondorder NLO properties were measured in different solvents. Absorption and emission spectra were
also measured, both in solution and in the solid state. Surprisingly, the synthesized molecule
showed a very high fluorescence quantum yield in both cases.
References
1. S. Varghese, S. Das, J. Phys. Chem. Lett. 2011, 2, 863-873.
2. E. Cariati, G. Cavallo, A. Forni, G. Leem, P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, S. Righetto, G.
Terraneo, E. Tordin, Cryst. Growth Des. 2011, 11, 5642-5648.
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P10
Desmotropy, polymorphism and solid-state proton transfer: four solid forms of
an aromatic o-hydroxy Schiff base
I. Ĉiloviü,1 M. Rubþiü,1 K. Užareviü,1,2 I. Halasz,1,2 N. Bregoviü,1 M. Mališ,2 Z. Kokan,2 R. S.
Stein,3 R. E. Dinnebier,4 V. Tomišiü1
1
Department of Chemistry,Faculty of Science, University of Zagreb, Horvatovac 102a, 10002
Zagreb, Croatia
2
Ruÿer Boškoviü Institute, Bijeniþka 54, 10002 Zagreb, Croatia
3
Bruker UK Ltd, Banner Lane, Coventry CV4 9GH, United Kingdom
4
Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569 Stuttgart, Germany
E-mail: [email protected]
The Schiff base derived from salicylaldehyde and 2-amino-3-hydroxypyridine affords diversity of
solid forms, two polymorphic pairs of the enol-imino (D1a and D1b) and keto-amino (D2a and
D2b) desmotropes.1 Isolated phases, identified by IR spectroscopy, X-ray crystallography and 13CP
MAS NMR, display essentially planar molecular conformations characterized by strong
intramolecular hydrogen bond of the O–HÂÂÂN (D1) or N–HÂÂÂO (D2) type. A change in the proton
position within this OÂÂÂHÂÂÂN system is accompanied by substantially different molecular
conformations, and subsequently with divergent supramolecular architectures. The appearance and
interconversion conditions for each of the four phases have been established on the basis of a
number of solution and solvent-free experiments, and evaluated against the results of computational
studies. Solid phases readily convert to the most stable form (D1a) upon exposure to methanol
vapor, heating or by mechanical treatment, and these transformations are accompanied by the
change in the sample color. The course of thermally induced transformations has been monitored in
detail by means of temperature-resolved X-ray powder diffraction and infrared spectroscopy. Upon
dissolution, all forms equilibrate immediately, as confirmed by NMR and UV-Vis spectroscopies in
several solvents, with the equilibrium shifted far towards the enol tautomer. This study reveals the
significance of peripheral groups in stabilization of metastable tautomers in the solid state.
References
1. a) P. Jacobson, Ber. Dtsch. Chem. Ges. 1887, XX, 1732; b) A. Hantzsch, F. Herrmann Ber. Dtsch. Chem.
Ges. 1887, XX, 2803; c) P. Jacobson, Ber. Dtsch. Chem. Ges. 1888, XXI, 2628; J. Elguero, Cryst. Growth
Des. 2011, 11, 4731-4738; d) C. Foces-Foces, A. L. Llamas-Saiz, R. M. Claramunt, C. Lopez, J. Elguero,
J. Chem. Soc., Chem. Commun. 1994, 1143-1145; e) P. Csomos, L. Fodor, A. Csampai, P. Sohar,
Tetrahedron 2010, 66, 3207-3213; f) T. Holczbauer, L. Fabian, P. Csomos, L. Fodor, A. Kalman,
CrystEngComm 2010, 12, 1712-1717; g) M. U. Schmidt, J. Brüning, J. Glinnemann, M. W. Hutzler, P.
Mörschel, S. N. Ivashevskaya, J. van de Streek, D. Braga, L. Maini, M. R. Chierotti, R. Gobetto, Angew.
Chem. Int. Ed. 2011, 50, 7924-7926.
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P11
Design, Synthesis and Characterization of luminescent copper(I)-iodide
complexes for optoelectronic devices
F. Farinella1, P. P. Mazzeo1, L. Maini1, D. Braga1
1
Dipartimento di chimica G.Caimician, Università di Bologna, via Selmi 2, 40126 ,Bologna,
E-mail: [email protected]
Phosphorescent emissive Ir-based complexes have been a large improvement in application for
OLEDs, because of their high quantum yield (Ir). Unfortunately, Ir is rare in natural abundance and
this increase the cost of production, hence the interest has moved to Copper-Iodide based
complexes because of their luminescence, low cost and stability in air. The luminescence of these
complexes comes both from the nature of the inorganic core and the nature of the ligand used. A
Low-Energy emission band called 3CC due to the Cu-Cu distance of about 2.8 Å is proper of these
complexes and if the ligand has accessible ʌ*-orbitals, an High-Energy emission band called
3
XLCT appear (2). Commonly, these complexes have mono-dentate ligands but we were interested
on bidentate ones (3) to study the chelating effect and to tune the luminescence properties by using
chemically different bonding site.For this reason we have synthesized and analyzed different
complexes of CuI and diphenyl-2-pyridyl phosphine in different conditions and stoichiometry ratio.
Extremely high quantum yield has been obtained with those complexes with a maximum of 85 %
recorded for compound 1 and preliminary experiment to pose this complex in thin film for
optoelectronic application has been performed.
Figure 1: diphenyl-2-pyridyl phosphine
References
1. Albertus J. Sandee,† Charlotte K. Williams,† Nicholas R. Evans,† John E. Davies Clare E. Boothby,‡
Anna Ko¨ hler,‡ Richard H. Friend,‡ and Andrew B. Holmes, J. Am. Chem. Soc 2004, 126, 7041-7048
2. Chong Kul Ryu, Marcello Vitale, and Peter C. Ford, Inorg. Chem. 1993, 32, 869-874.
3. Daniel M. Zink, Michael Bächle, Thomas Baumann, Martin Nieger, Michael Kühn, Cong Wang, Wim
Klopper, Uwe Monkowius, Thomas Hofbeck, Hartmut Yersin,and Stefan Bräse, Inorg. Chem. 2013, 52,
2292-2305
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P12
Organic frameworks formed via hydrogen and halogen bonding
orthogonal self-assembly
F. Fernandez-Palacio,a L. Colombo,ab J. Martí-Rujas,b G. Terraneo,ab T. Pilati,a
P. Metrangolo,ab G. Resnati.ab
a
NFMLab, Department of Chemistry, Materials, and Chemical
Engineering, Politecnico di Milano, via Mancinelli 7, 20131 Milan, Italy
b
Center for Nano Science and Technology@Polimi, Istituto Italiano
di Tecnologia, Via Pascoli 70/3, 20133 Milano, Italy.
E-mail: [email protected]
Self-assembly of metals (nodes) and organic ligands (linkers) is a widely exploited strategy
for the synthesis of materials with extended network structures. The self-assembly relying on
different, noninterfering intermolecular interactions is attracting considerable interest as a strategy
to obtain “smarter” stimuli-responsive materials. The combination of two or more orthogonal
supramolecular synthons resulted, in fact, in a range of novel materials like switchable
supramolecular copolymers, chiral bimetallic self-supported hydrogenation catalysts, voltageresponsive vesicles, and self-assembled fibrillar networks.1 Orthogonal self-assembly has also
yielded functional monolayer architectures, as well as the improvement of bulk material properties.
Ionic interactions, metalíligand complexation, and hydrogen bonds are most frequently combined
in driving orthogonal self-assembly processes.
In our recent work2 has been demonstrated that hydrogen bonding (HB) and halogen
bonding (XB),3 which most often are seen in competition, can cooperate orthogonally in building up
open organic frameworks. The flexibility of the obtained open framework has allowed hosting
various guest molecules. To tune the porosity of the XB-HB network we have designed new rigid
ligands which have two pairs of sites that can work as prototypical XB or HB donor/acceptor
groups. In this communication we report preliminary results of this research.
References
1. S. K. Yang, A. V. Ambade, M. Weck, Chem. Soc. Rev. 2011, 40, 129í137.
2. J. Martí.Rujas, L. Colombo, J. Lü, A. Dey, G. Terraneo, P. Metrangolo, T. Pillati, G. Resnati. Chem.
Commun., 2012, 48, 8207–8209
3. P. Metrangolo, H. Neukirch, T. Pilati and G. Resnati, Acc. Chem. Res., 2005, 38, 385–395
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P13
LCDiXRay: Powder diffraction indexing of Columnar Liquid Crystals
N. Godbert1, A. Crispini1, M. Ghedini1, M. Carini2,3, F. Chiaravalotti4, A. Ferrise5
Centro di Eccelenza CEMIF.CAL, LASCAMM CR-INSTM della Calabria, Dipartimento di
Chimica e Tecnologie Chimiche, Università della Calabria, 87036 Arcavacata di Rende (CS), Italy
2
Dipartimento di Ingegneria per l’Ambiente ed il Territorio e Ingegneria Chimica, Università
della Calabria, 87036 Arcavacata di Rende (CS), Italy
3
INFN- Cosenza Unit, Arcavacata di Rende I-87036, Cosenza, Italy
4
Dipartimento di Fisica, Università della Calabria, 87036 Arcavacata di Rende (CS), Italy
5
Dipartimento di Informatica, Modellistica, Elettronica e Sistemistica, Università della Calabria,
87036 Arcavacata di Rende (CS), Italy
...
E-mail: [email protected]
1
The present contribution will introduce in “avant-première” LCDiXRay[1] our newly developed
standard computerized procedure for the indexation of X-Ray Powder Diffraction (PXRD) patterns
of columnar liquid crystals. This user-friendly software implemented in an objected-oriented
framework has been included in a Java GUI program. The model generation based on the observed
diffraction pattern will allow the straightforward identification of columnar liquid-crystal
mesophase symmetry - Hexagonal (Colh), Rectangular (Colr), or Oblique (Colo) as well as the
determination of all structural information extracted from a properly indexed PXRD spectrum. In
particular, the proposed program notably accelerates, the identification of columnar mesophases
together with the in situ determination of their structural parameters such as: mesophase type, space
group, cell dimension, cross section area, intermolecular stacking distance between consecutive
discoids, and in the case of ordered mesophases, the estimation of the number of molecules
constituting each discoid.
References
1. N. Godbert, A. Crispini, M. Ghedini, M. Carini, F. Chiaravalotti and A. Fernise, Journal Of Applied
Crystallography, 2013, submitted.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P14
Real-time in situ X-ray diffraction monitoring of mechanochemical formation of
model organic pharmaceutical cocrystal
I. Halasz1, A. Puškariü1, S. A. J. Kimber2, P. J. Beldon3, F. Adams4,
V. Honkimäki2, R. E. Dinnebier4, V. Štrukil,1,5 T. Frišþiü5
1
Rudjer Boškoviü Institute, Zagreb, Croatia
2
European Synchrotron Radiation Facility (ESRF), Grenoble, France
3
Department of Chemistry, University of Cambridge, Cambridge, UK
4
Max-Planck-Institute for Solid State Research, Stuttgart, Germany
5
Department of Chemistry, McGill University, Montreal, Canada
E-mail: [email protected]
A persistent obstacle in the study of millling reactions has been the inability to directly monitor their
course. As a result, mechanochemical reaction mechanisms were studied in a stepwise fashion by
stopping the milling at designated times and subsequently analyzing the reaction mixture. We
recently described the first, non-invasive and potentially general methodology for real-time, in situ
monitoring of milling reactions by powder X-ray diffraction (PXRD).[1] This technique is enabled
by high-energy (O=0.1427 Å, E = 86 KeV) X-rays capable of penetrating the walls of the milling
vessel and interacting with the sample within while the mill is operating.
The methodology has been demonstrated on metal-organic frameworks but its applicability is
broader and encompasses materials of various scattering powers. Here we present the ability to
conduct real-time and in situ X-ray diffraction monitoring of mechanochemical transformations
involving purely organic, pharmaceutically relevant, solids. The in situ technique demonstrated the
surprising speed of cocrystal formation in liquid-assisted grinding (LAG), as compared to
amorphisation in neat grinding, yielding almost 0.5 gram of the pharmaceutical cocrystal of
carbamazepine and saccharin within 2 minutes.
Figure 1. Molecular structures of cocrystal components, carbamazepine (cbz) and saccharine (sacc) and
time-resolved diffractograms of neat and liquid-assisted grinding.
References
1. T. Frišþiü, I. Halasz, P. J. Beldon, A. M. Belenguer, F. Adams, S. A. J. Kimber, V. Honkimäki,
R. E. Dinnebier Nature Chem., 2013, 5, 66-73.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P15
Structural Studies of Supramolecular Gyroscope-like Co-crystals
J. Lin1, C. M. Widdifield2, G. Cavallo1, G. A. Facey2, T. Pilati1, P. Metrangolo1, G. Resnati1, D. L.
Bryce2
1
NFMLab – D.C.M.I.C. “Giulio Natta”, Politechnico di Milano, Milano, Italy.
2
Department of Chemistry and Centre for Catalysis Research and Innovation, University of
Ottawa, Ottawa, Ontario, Canada.
E-mail: [email protected]
The construction of small-sized devices has attracted great amount of research interest for decades.
Among these researches, rational design and synthesis of molecular devices based on
supramolecules are fascinating topics [1]. In our attempts to design and synthesis of supramolecular
gyroscopes
[2],
co-crystals
between
decamethonium
diiodide
(i.e.,
[(CH3)3N+(CH2)10N+(CH3)3][2Ií]) and different para-dihalogen-substituted benzene moieties (i.e.,
p-C6X2Y4, X = Br, I; Y = H, F) are obtained. Single-crystal X-ray diffraction (XRD) structures of
three novel co-crystals exhibit supramolecular gyroscope-like structures constructed by halogen
bonding of 1:1 stoichiometry of two components [3]. Variable-temperature 19F NMR experiments
are used to distinguish between dynamic and static disorder of rotor in selected product materials.
The variable-temperature 19F NMR spectra of co-crystals are insensitive to temperature, other than
some very small shift changes (< 2 ppm over the full range of temperature). There are no
discernible line width changes in this temperature range, which suggests that dynamic disorder of
the rings is unlikely.
Figure 1: Crystal packing of decamethonium diiodide / I-(C6F4)-I adduct, viewed along b axis(top) and along c axis
(bottom).
References
1. R. Ballardini, V. Balzani, A. Credi, M.T. Gandolfi, M. Venturi Acc. Chem. Res. 2001, 34, 445–455, and
references therein.
2. C. Lemouchi, C. S. Vogelsberg, L. Zorina, S. Simonov, P. Batail, S. Brown, M.A. Garcia-Garibay J. Am.
Chem. Soc. 2011, 133, 6371–6379.
3. a) P. Metrangolo, G. Resnati, Chem. Eur. J. 2001, 1, 2511-2519; b) P. Metrangolo, F. Meyer, T. Pilati, G.
Resnati, G. Terraneo, Angew. Chem. Int. Ed. 2008, 47, 6114-6127; c) G. Cavallo, P. Metrangolo, T.
Pilati, G. Resnati, M. Sansotera, G. Terraneo, Chem. Soc. Rev. 2010, 39, 3772-3783.
6-7 June 2013, Milan, Italy
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P16
On the role of hydrogen bond in the crystal packing of Ru (II) half-sandwich
complexes
C. Loffi, P. Pelagatti, A. Bacchi, P. Swuec
Dipartimento di Chimica, Università degli Studi di Parma, Parco Area Scienze 17/A, 43124 Parma,
Italy
[email protected]
The aim of this work is the study of the supramolecular interactions present in the crystalline
networks of half-sandwich Ru (II) complexes, potentially able to give rise to Wheel-And-AxleMetallorganic (WAAMO) compounds [1]. These consist of molecular entities made by two wheels
represented by organometallic half-sandwich units [(p-cimene)RuCl2] connected by an axle (formed
by the dimerization of COOH or C(O)NH2 groups) [2]. One of the most recurrent synthons
involving these functional groups is the cyclic dimer R22(8). The compounds studied in this work
are [Ru(p-cymene)(p-amino benzamide)Cl2] (1) and {Ru(p-cymene) [3-(4-aminophenyl)propionic
acid]Cl2} (2). Their synthesis was carried out in dry methanol under dry nitrogen, starting from the
dimer [Ru(Ș6-p-cimene)Cl2] 2 and the free ligands p-amino benzamide or 3-(4-aminophenyl)
propionic acid. Crystals of 1 were collected from methanol and the XRD analysis of a single crystal
revealed the presence of the desired R22(8) cyclic dimer involving the amide functions (Figure 1,
left). Diversely, the XRD analysis of a single crystal of 2 grown in THF showed the formation of
supramolecular chains sustained by strong C=O…N-H e O-H…Cl intermolecular hydrogen bonds
between the COOH function of a molecule and the amine group and a chloride ligand of a
neighboring molecule (Figure 1, right). In both cases, the analysis of the crystal packing evidences
the role of hydrogen-bond accepting group played by the chloride ligands which, in the case of
complex 2, impedes the cyclic dimerization of the COOH functions [3].
Figure 1: Dimerization of the amidic functions in complex 1 (left) and intermolecular hydrogen bonds involving Cl
ligands in complex 2 (right).
References
1. A. Bacchi, M. Carcelli, P. Pelagatti Crystallogr. Rev. 2012, 18, 1-27
2. A. Bacchi, P. Pelagatti et al. Cryst. Growth Des. 2011, 11, 5039-5047
3. A. Bacchi, P. Pelagatti et al. CrystEngCom. 2011, 13, 4365-4375
6-7 June 2013, Milan, Italy
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P17
A Voyage In The B Vitamins World: B6 As Novel Ligand In Cluster Chemistry
And New Discoveries In The Field Of B12 Crystallography.
N. Marino,1,2 D. Armentano1, G. De Munno,1 R. P. Doyle2
Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, Italy
3
Department of Chemistry, Syracuse University, Syracuse, NY 13244-4100, United States
1
E-mail: [email protected]; [email protected]
Presented herein are a couple of crystallographically interesting examples (small molecule vs. 'large'
small molecule) featuring either vitamin B6 (pyridoxine, PN-H) or B12 (cyanocobalamin, CNCbl),
the former as novel and versatile ligand in cluster chemistry, and the latter in a unique protonated
form offering up the occasion to examine and discuss the influence of crystal packing forces in
cobalamins' structures. In particular:
I. By using vitamin B6 in its mono-deprotonated pyridoxine form (PN-H-) [PN = 3-hydroxy-4,5bis(hydroxymethyl)-2-methylpyridine], we have synthesized and magneto-structurally characterized
two
tetranuclear
MnII2MnIII2
and
CuII4
compounds
of
formula
[Mn4(PNH)4(CH3CO2)3Cl2]Cl·2CH3OH·2H2O and [Cu4(PN-H)4Cl2(H2O)2]Cl2, showing the ability of B6 to
act as unusual but suitable ligand toward the self-assembling of cubane moieties [1].
II. In the course of experiments directed toward the synthesis of vitamin B12-bioconjugates for drugdelivery purposes, we observed the formation of well-shaped red parallelepipeds from a
concentrated aqueous solution of the HPLC-purified vitamin. The crystals were investigated
classically by using MoKĮ radiation at 98 K, and they turned out to be an unprecedented CNCbltrifluoracetate salt. By comparing this structure with other CNCbls reported in the literature, we
noted significant differences in the upward fold angle of the corrin macrocycle, which could only be
justified by assuming the existence of a strong relationship between crystal packing forces and
cobalamins' molecular structure, as mostly ignored in the field of B12 crystallography so far [2].
Figure 1: Left. A view of the cationic unit in complex [Cu4(PN-H)4Cl2(H2O)2]Cl2; H-atoms omitted for clarity. Right. A
view of the isolated CNCbl(H)+ cation.
References
1. N. Marino, D. Armentano, T.F. Mastropietro, M. Julve, G. De Munno, J. Martínez-Lillo, in prep for Cryst.
Growth Des. (2013).
2. N. Marino, A. E. Rabideau, R. P. Doyle, Inorg. Chem. 2011, 50, 220-230.
6-7 June 2013, Milan, Italy
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P18
Supramolecular Gels formation induced by Halogen Bonding
1
L. Meazza,1 J. A. Foster,2 K.Fucke,2 P.Metrangolo,1 G. Resnati,1 J. W. Steed.2
NFMLab-DCMIC "Giulio Natta", Politecnico di Milano, Via L. Mancinelli 7, IT-20131, and
CNST-IIT@POLIMI, Via G. Pascoli 70/3, IT-20133, Milano, Italy
2
Department of Chemistry, Durham University, South Road, Durham, DH1 3LE
[email protected]
Tunable gel phase materials are an emerging topic of interest in potential applications in many
various fields [1,2]. Within this context low molecular weight supramolecular gelators (LMWG),
with their reversible and dynamic intermolecular interactions, are achieving increasing prominence.
As a starting point we focused our attention on metallogels, in which the metal coordination results
in metal binding to the pyridyl group of pyridyl-urea compounds, which suppresses the alternative,
gel-inhibiting, urea-pyridyl hydrogen bonding interaction, freeing the urea groups to form fibrils
and hence gels (figure 1a) [3].
In this communication we will show that halogen bonding is sufficiently strong to competitively
interfere with inhibitory urea-pyridyl hydrogen bonding in order to favor fiber formation and hence
gelation in a similar way to metal coordination giving the first example of application of halogen
bonding in order to control and “switch on” gelation (figure 1b) [4].
Once demonstrated that halogen bonding induced gelation is a general phenomenon we designed a
halogen bonding donor gelator combining bis(urea) and perfluoroaryliodide components in the
same molecule (figure 1c) and we “turned on” gelation simply by adding 4,4’-bipyridine, a strong
halogen bonding acceptor (figure 1c,d) [5].
Figure 1: a) Metal coordination frees the urea moieties to produce parallel gel-forming Į-tape motifs. b) X-ray crystal
structure of the halogen bonded gel showing the gel-forming urea-tape interaction and the halogen bonding cross-links
involving the pyridyl groups (using 1,4-diiodotetrafluorobenzene as halogen bonding-donor molecule). c) Chemical
structure of the new halogen bonding donor gelator (XB-Gelator) and the acceptor 4,4’-bipyridine. d) A 1% solution of
the XB-Gelator (left) and the same solution with the addition of 4,4’-bipyridine which drives the gel formation (right).
References
1. H. Li, Y. Fujiki, K. Sada, L. A. Estroff, CrystEngComm 2011, 13, 1060-1062.
2. B. Escuder, F. Rodríguez-Llansola, J. F. Miravet, New J. Chem. 2010, 34, 1044-1054.
3. P. Byrne, G. O. Lloyd , L. Applegarth, K. M. Anderson, N. Clarke, J. W. Steed, New J. Chem. 2010, 34,
2261-2274.
4. P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, Angew. Chem. Int. Ed. 2008, 47, 6114-6127.
5. L. Meazza, J. A. Foster, K. Fucke, P. Metrangolo, G. Resnati, J. W. Steed, Nature Chem. 2013, 5, 42-47.
6-7 June 2013, Milan, Italy
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P19
Polymorphism And Solid Forms In 1,1,4,4-Tetraphenyl-1,3-Butadiene.
A. Monica1, A. Bacchi1, M. Masino1, D. Crocco1
1
Università degli Studi di Parma, Parma, Italy
E-mail: [email protected]
1,1,4,4-Tetraphenyl-1,3-butadiene (TPB) is an efficient blue emitting material. It is currently known
in four distinct polymorphs and a solvate form with cyclehexanone. Our study focused on obtaining
Ȗ and į polymorphs and the solvate form. The latter crystallizes from a saturated solution of TPB in
cyclehexanone. We found a protocol to obtain the į polymorph melting the commercial product and
cooling it on a hot stage at temperature gradients faster than 0,5 °C/min, otherwise it crystallizes as
the Į polymorph. This suggests that the į phase is the kinetic one whereas the Į is the
thermodynamically stable one. Ȗ crystals were obtained by evaporation and epitaxial crystallization
on Ȗ crystals previously obtained but so far there is no protocol to crystallize them from solution or
molten TPB. The characterization techniques applied to identify the crystals have been powder and
single crystal X-ray diffraction. Solid state NRM spectroscopy gave us a further confirmation of the
different packing in the crystals and showed the evolution of the solvate form at different times. In
the investigation of the crystals obtained we focused our attention on the use of Raman
spectroscopy, which is becoming more and more common in the identification of polymorphs. This
is due to the differences in the spectra both in the intermolecular (lattice) and intramolecular
vibrations, ascribed to different molecular conformations. [1]
Figure 1: Raman spectra of į, Ȗ and Į polymorphs.
References
1. A. Girlando, S. Ianelli, I, Bilotti, A. Brillante, R. G. Della Valle, E. Venuti, M. Campione, S, Mora, L.
Silvestri, P, Spearman, S. Tavazzi, Crystal Growth and Design, 2010, Vol, 10, 2752-2758
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P20
Picturing the induced fit of calix[5]arenes upon n-alkylammonium cation
binding
A. Notti,1 G. Gattuso,1 S. Pappalardo,2 M. F. Parisi,1 T. Pilati,3 G. Resnati,3 G. Terraneo3
1
Dipartimento di Scienze Chimiche, Università di Messina, viale F. Stagno d’Alcontres 31, 98166
Messina, Italy
2
Dipartimento di Scienze Chimiche, Università di Catania, viale A. Doria 6, 95125 Catania, Italy
3
NFMLab, Dipartimento di Chimica, Materiali ed Ingegneria Chimica ‘‘Giulio Natta’’, Politecnico
di Milano, via L. Mancinelli 7, 20131 Milano, Italy
E-mail: [email protected]
The serendipitous crystallization of a 1:1 endo-cavity complex between penta-ester calix[5]arene 1a
[1] and n-butylammonium ions sheds light on the conformational rearrangement –from cone-in to
cone-out– this calixarene family undergoes upon guest inclusion [2]. A coordinated (if not
concerted) motion of the aryl rings upon complexation can be envisaged to describe the endo-cavity
inclusion process of alkylammonium ions (Figure 1). On going from the ‘empty’ to the ‘filled’
forms, an overall structural rearrangement takes place to match the geometrical and stereoelectronic
requirements of the guest. Close comparison of the solid-state structures of two alkylammonium
ion-calix[5]arene complexes reveals that the nature of the lower rim substituents (i.e. ester vs alkyl
groups [3]) significantly influences the depth of endo-cavity penetration of the guest and ultimately
the receptor strength.
Figure 1: Solid-state structures of calix[5]arene 1a and the corresponding n-BuNH3+1a complex.
References
1. G. Barrett, M. A. McKervey, J. F. Malone, A. Walker, F. Arnaud-Neu, L. Guerra, M.-J. Schwing-Weill,
J. Chem. Soc., Perkin Trans. 2 1993, 1475–1479.
2. G. Gattuso, A. Notti, S. Pappalardo, M. F. Parisi, T. Pilati, G. Terraneo, CrystEngComm 2012, 14, 2621–
2625.
3. G. Gattuso, A. Notti, S. Pappalardo, M. F. Parisi, T. Pilati, G. Resnati, G. Terraneo, CrystEngComm
2009, 11, 1204–1206.
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P21
Travelling with Polymorphs: the Case of Tetrapentoxycalix[4]arene
A. G. Ricciardulli1, M. Lusi2, L. Erra3, C. Gaeta,1 C. Talotta,1 P. Neri,1 L. J. Barbour2, C. Tedesco1
1
Dipartimento di Chimica e Biologia, Università degli Studi di Salerno, Fisciano, Italy
2
Dept. of Chemistry and Polymer Science, University of Stellenbosch,
Stellenbosch, South Africa
3
ESRF, Grenoble, France
E-mail: [email protected]
Polymorphism, the existence of more than one crystalline form of a compound, is very actively
studied [1,2]. In the framework of a bilateral exchange programme between Italy and South Africa
tetrapentoxycalix[4]arene (1) was synthesized and structurally characterized. Needle-shaped single
crystals of 1 were obtained by slowly cooling a dichloromethane/methanol solution. The unit cell is
monoclinic with c axis of 21.287(4) Å and smaller values for a and b axis, respectively of 12.243(2)
Å and 7.785(1) Å, and contains calixarene 1 in a 1,3-alternate conformation. The packing is
characterized by the formation of parallelepipeds of indefinite length composed by superposed
calixarenes, which are set parallel and antiparallel to the b axis (see Figure 1a). Each calixarene
interacts by CH-ʌ van der Waals interactions with the following one to give a supramolecular
nanotube.
Polymorphic behaviour emerged after sending a sample to the University of Stellenbosch for further
studies. This prompted us to perform variable temperature X-ray diffraction studies both on single
crystals and powders. Hot stage microscopy and thermal analyses were also used to assess the
reversible phase transition, which occurs at 70 °C.
Figure 1: a) Crystal packing of
tetrapentoxycalix[4]arene 1 at room temperature; b) Hot-stage microscopy images showing the phase transition at 70
°C.
Funding by Italian Ministry for Foreign Affairs and National Research Foundation is gratefully
acknowledged.
References
1. J. Dunitz, J. Bernstein, Acc. Chem. Res. 1995, 28, 193-200.
2. J. Bernstein, Polymorphism in Molecular Crystals, OUP, Oxford, 2002.
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P22
Functional group effect on the clathrating properties of half-sandwich Ru (II)
complex
F. Scè, A. Bacchi, P. Pelagatti
Department of Chemistry, University of Parma, Parco Area Scienze 17/A, 43124 Parma, Italy
E-mail: [email protected]
This work deals with the role played by functional groups on the clathrating properties of two
metallorganic complexes, chosen owing to their potential ability to build up supramolecular
architectures called Wheel-and-Axle Metallorganics, interesting for their clathrating properties(1).
Both complexes contain half-sandwich Ru(II) units (thought as the wheels) and differ in the ligands
used to form the supramolecular axle: 4-(4-amino phenyl) butyric acid (1) and 4-aminobenzanilide
(2). The choice of these ligands is due to the fact that the synthetized complexes have a balance
between the number of hydrogen bond donor and acceptor functions (2), in order to make easier the
dimerization of the carboxylic and amide groups. These results allow to evaluate the influence the
length of the spacer has onto the formation of the WAAMO and its clathrating properties, once
compared with already reported systems(2). On the other hand the amidic H in the amino-amidic
ligand is a good acceptor of hydrogen bonds, so that it may catch volatile guests (3).
The syntheses were carried out in dry MeOH and the products were crystallized by slow
evaporation from the reaction solvent. The complexes were characterized by IR, 1HNMR, TGA and
elemental analysis. XRD analysis on single crystals of both complexes showed the absence of the
expected dimer. The crystalline structure of 1 resulted inert towards the inclusion of volatile guests,
while complex 2 showed the ability of including a molecule of H2O thanks to an intermolecular
interaction with the amidic group: this turned out to be a good hydrogen bond donor and could be
the basis for other works, using other volatile guests.
Figure 1 : Crystal packing of complex 1 Figure 2: Hydrogen bonds of H2O in complex 2
References
1. A.Bacchi, G.Cantoni, M. R. Chierotti, A.Girlando, R.Gobetto, G.Lapadula, P.Pelagatti, A.Sironi and
M.Zecchini “Water vapour uptake and extrusion by a crystalline metallorganic solid based on halfsandwich Ru(II) building-blocks” CrystEngComm 2011
2. A.Bacchi, G.Cantoni, M.Granelli, S.Mazza, P.Pelagatti and G.Rispoli “Hydrogen bond optimization via
molecular design for fabrication of crystalline organometallic Wheel-and-Axle Compounds based on Half
Sandwich Ru (II) Units” Crystal Growth & Design 2011
3. C.B. Aakeröy, B.M.T. Scott, J. Desper New J. Chem. 2007 31 2044-2051
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P23
Pt(II)-imino derivatives: dimers and oligomers
as a supply of cytotoxic agents
P. Sgarbossa1, R.A. Michelin1, R. Bertani1, M. Mozzon1,
C. Marzano2, V. Gandin2
1
Department of Industrial Engineering,UNIPD, Via F. Marzolo, 9, 35131 Padua, Italy;
2
Department of Pharmaceutical Sciences, UNIPD, Via F. Marzolo 5, I-35131 Padua, Italy
.
[email protected]
A class of relevant biologically active Pt(II)-based drugs1 has been prepared from the synthetically
useful organonitrile Pt(II) complexes cis- and trans-[PtCl2(NCR)2] (R = Me,Ph,CH2Ph) by taking
advantage of their ability to undergo nucleophilic addition of alcohols, amines and thiols at the C{N
triple bond2 affording iminoether, amidine and iminothioether3 derivatives, respectively. The
configuration of the reaction products can be either Z or E corresponding to the trans or cis addition
of the protic nucleophile along the C{N triple bond, respectively.
The X-Ray structures of some of these derivatives show that four N-H˜˜˜Cl intermolecular contacts
between each chlorine atom and the N-H proton of the imino ligand (L) give Pt2Cl4L4 dimers
formed by two centrosymmetrically related PtCl2L2 units or oligomers. These latter are evidenced
also by ESI MS determinations.
Figure 1. ORTEP drawing of a dimer of compound trans[PtCl2^E-N(H)=C(SEt)CH2Ph`2]
Figure 2. ORTEP drawing of the oligomeric
compound trans-[PtCl2^E-N(H)=C(NMe)M`2]
ESI MS and NMR studies indicate the dependence of the association processes from concentration
and the nature of the medium. The formation of dimeric or oligomeric species could play a role in
the concentration dependence of their hydrolysis rate in the biological tests. This aspect has been
previously investigated as for the stability of infusion solutions of carboplatin and oxaliplatin.
References
1. R.A. Michelin, P. Sgarbossa, S.M. Sbovata,V. Gandin,C. Marzano, R. Bertani,CHEMMEDCHEM 2011,
6, 1172-1183.
2. R.A. Michelin, M. Mozzon, R. Bertani, Coord.Chem.Rev.1996, 147, 299-338.
3. P. Sgarbossa, S.M. Sbovata, R. Bertani, M. Mozzon, F. Benetollo, C. Marzano, V. Gandin, R.A.
Michelin, Inorg.Chem. 2013, DOI: 10.1021/ic3024452
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P24
ZnO nanoparticles synthesis with controlled morphology (shape & size) by using
natural biodegradable polymer
S. U. Shisodia1, A. Citterio1, V. V. Chabukswar2*, N. S. Pande3, V. Purohit3, S. V. Bhavsar2, K. N.
Hondore2, K. C. Mohite4,
1
Department of CMIC,“Giulio Natta”, Politecnico di Milano, Milan, Italy.
Department of Chemistry, Nowrosjee Wadia College, University of Pune, Pune, India.
3
Symbiosis International University, Symbiosis Institute of Technology, Pune, India.
4
Department of Physics, Haribhai Desai College, University of Pune, Pune, India.
2
E-mail: [email protected]
Natural biodegradable polymer is used for the controlled synthesis of hexagonal shape ZnO
nanoparticles of 20-30 nm diameter size. The factors affecting such as reaction time and
concentration of precursor which play a major role on the nature and growth of ZnO nanoparticles
are well studied, nanoparticles are characterized by X-ray diffraction, SEM, TEM, FTIR, EDAX,
UV and Raman spectroscopy analysis [1]. ZnO nanoparticles have generated a potential research
interest in the recent years owing to the wide range of applications in a variety of areas, including
physics, chemistry, electronics, optics, materials science, and the biomedical sciences due to their
flexibility of preparations in different morphologies with different shape, size and properties [2,3].
For the synthesis of ZnO nanoparticles different techniques used such as sol-gel, combustion,
precipitation, hydrothermal, solvothermal, chemical vapor deposition and microwave assisted
thermal oxidation [2,3]. We have developed environmental friendly method for the synthesis of
hexagonal shape ZnO nanoparticles by using a novel green route at room temperature in aqueous
medium, from inexpensive, biodegradable plant origin natural polymer Gum Tragacanth as a
binder. This novel synthesis is facile and scalable to produce bulk quantity of ZnO nanoparticles on
industrial scale.
Figure 1: a) TEM micrographs of Hexagonal ZnO nanoparticals, b) Powder X-ray diffraction pattern of hexagonal ZnO
nanoparticles and ZnO bulk nanoparticles.
References
1.
2.
3.
V.V. Chabukswar, et al. submitted to Jou. of Materials Chemistry and Physics 2013.
M.B. Cortie, et al. Chemical Engineering Journal 2012, 185–186, 1– 22.
P.J.P. Espitia & N.F.F. Soares, et al. Food Bioprocess Technol 2012, 5, 1447–1464.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P25
Crystallization Of Two Isomeric Aminoacids From Solution And From Gel
F. Silvestri, D. Crocco, A. Bacchi
Dipartment of Chemistry, Universtity of Parma, Parma, Italy
[email protected]
Our purpose is to study the solid state behaviour of the two organic molecules, 4-amino-3hydroxybenzoic acid (4A3HBA) and 3-amino-4-hydroxybenzoic acid (3A4HBA), that have been
extensively used by our research group as ligands in coordination chemistry.
The two aminoacids have been crystallized using two methods: crystallization from gel and from
solution, two different ways that required different solvents. After obtaining single crystals suitable
for X-ray diffraction, we observed that 4A3HBA comes out every time in anhydrous form (Fig. 1).
The 3A4HBA acted differently, crystallizing in a monohydrated zwitterionic form (Fig. 3). In fact
an inert atmosphere of dry nitrogen was necessary in order to obtain the anhydrous form (Fig. 2).
Figure 1. Crystal packing of 4A3HBA Figure 2. Crystal packing of 3A4HBA
Figure 3. Crystal packing of 3A4HBA·H2O
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P26
A Nanoporous Crystalline Structure Generated by a Tiourea-based
Calix[6]arene
F.Ugozzoli, A. Arduini, R. Bussolati, C. Massera, F. Rapaccioli, A. Secchi
Dipartimento di Chimica, Parco Area delle Scienze 17/A, 43124 Italy
E-mail: [email protected]
Calix[n]arenes have been extensively studied in the past years as receptors for ions and neutral
molecules as well as for the construction of self-assembled supramolecular species by use of noncovalent intermolecular interactions [1]. In previous papers, it has been demonstrated that
heteroditopic calix[4]arene and calix[6]arene derivatives may give rise to self-assembled capsules
[2] and oriented channels [3] in the solid state. The presence of phenylurea moieties on the wide rim
of these macrocycles has a great influence on both the conformational preferences of these
molecules and on the tuning of their self-assembly properties. Indeed, it has been shown via solid
state analysis on single crystals and quantum mechanical studies that the thiourea-based
calix[6]arene compound depicted in Figure 1 can self-organize in one-dimensional polymeric
chains via multiple intra- and intermolecular hydrogen bonds. A nanoporous crystalline structure is
generated as “tertiary structure” by the self-assembly of the polymeric chains in the crystal lattice.
Figure 1: Left: Structure formula of the thiourea-based calix[6]arene. Right: nanoporous crystalline structure.
References
1. C. D Gutsche, Calixarenes Revisited, Monograph in Supramolecular Chemistry, J. F. Stoddart Ed., The
Royal Society of Chemistry, 1998.
2. L. Pescatori, A. Arduini, A. Pochini, A. Secchi, C. Massera, F. Ugozzoli, CrystEngComm, 2009, 11, 239241.
3. A. Arduini, A. Credi, G. Faimani, C. Massera, A. Pochini, A. Secchi, M. Semeraro, S. Silvi, F. Ugozzoli,
Chem. Eur. J., 2008, 14, 98-106.
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
P27
Selective Mechanochemistry: Flexible Molecular Receptors for Recognition of
Organic Isomers in Milling Processes
K. Užareviü,1 I. Halasz,1 I. Ĉiloviü,2 M. Rubþiü,2 N. Bregoviü2
1
Ruÿer Boškoviü Institute, Bijeniþka 54a, Zagreb, Croatia
2
Faculty of Science, Horvatovac 102a, Zagreb, Croatia
E-mail: [email protected]
Molecular recognition [1], a process which emerges from weak non-covalent interactions, is of
paramount importance in the chemistry of life and also for the design of functional supramolecular
systems. Selective molecular recognition is traditionally performed in solution, where the host and
guest have mobility to come close and to interact. However, recent advances in the field of
mechanochemistry have shown that various concepts of supramolecular chemistry can be used also
for solvent-free reactions.[2] Herein we present flexible polyamine host[3](L) which recognizes and
selectively binds maleic acid during the milling with solid mixtures where the fumaric acid or other
investigated competitors were present in large excess.[4] During the recognition, L adapts its
conformation and forms specific complex with each of the six investigated dicarboxylic acids,
regardless of whether the reaction was conducted in solution or in the solid state. Recognition via
mechanochemistry involves intermediate phases, resulting with the same selectivity as achieved by
crystallisation from solution. Milling techniques circumvent limitations of solution-based
separation, as evidenced by facile binding of poorly soluble guests, while at the same time
providing enough energy and mobility to the host and guest molecules required for selective
recognition. Taken together, these results indicate a great potential of molecular recognition in the
solid state for separation purposes.
Figure 1: a) Host L and investigated isomeric dicarboxylic acids; supramolecular complexes of L with b) phthalic and
maleic acid, c) fumaric, succinic and terephthalic acid and d) isophthalic acid.
References
1. J.-M. Lehn, in Supramolecular Chemistry: Concepts and Perspectives, Wiley-VCH, 1995;
2. T. Frišþiü, Chem. Soc. Rev. 2012, 41, 3493-3510.
3. K. Užareviü, I. Ĉiloviü, D. Matkoviü-ýalogoviü, D. Šišak, M. Cindriü, Angew. Chem. Int. Ed. 2008, 47,
7022-7025.
4. K. Užareviü, I. Halasz, I. Ĉiloviü, N. Bregoviü, M. Rubþiü, D. Matkoviü-ýalogoviü, V. Tomišiü, Angew.
Chem. Int. Ed. 2013, 52, 5504-5508.
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
POSTER PRIZE WINNERS
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
ACS Publications - Crystal Growth and Design Poster Prizes:
Krunoslav Užareviü (P27)
Ruÿer Boškoviü Institute, Croatia
Selective Mechanochemistry: Flexible Molecular Receptors for Recognition of Organic Isomers in
Milling Processes
Andrea Monica (P19)
Università degli Studi di Parma, Italy
Polymorphism And Solid Forms In 1,1,4,4-Tetraphenyl-1,3-Butadiene.
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
RSC Publishing - CrystEngComm Poster Prizes:
Nadia Marino (P17)
Università della Calabria, Italy & Syracuse University, U.S.A
A Voyage In The B Vitamins World: B6 As Novel Ligand In Cluster Chemistry And New
Discoveries In The Field Of B12 Crystallography.
Jinxiang Lin (P15)
Politecnico di Milano, Italy
Structural Studies of Supramolecular Gyroscope-like Co-crystals
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
FluorIT Poster Prize:
Luca Catalano (P7)
Università di Bologna, Italy
Activation of room temperature phosphorescence of organic co-crystals. A novel approach based on
Halogen-Bond.
AICIng Poster Prize:
Irene Bassanetti (P1)
University of Milano Bicocca, Italy
Supramolecular Interactions as Glue for the design of Smart Architectures
6-7 June 2013, Milan, Italy
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PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
AUTHOR INDEX
6-7 June 2013, Milan, Italy
73
PAST, PRESENT, AND FUTURE OF CRYSTALLOGRAPHY@POLITECNICO DI MILANO
FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
A
F. Adams
L. Addadi
I. Aiello
A. Akiva
S. Aldrighetti
A. Arduini
D. Armentano
p. 55
p. 26
p. 12
p. 26
p. 46
p. 67
p. 58
B
A. Bacchi
L. Baldini
L. J. Barbour
I. Bassanetti
P. J. Beldon
M. Beretta
R. Bertani
S. Bertella
G. Berti
A. Bertocco
S. V. Bhavsar
E. Biavardi
R. Boese
S. Bracco
D. Braga
N. Bregoviü
D. L. Bryce
R. Bussolati
p. 23, 57, 60, 63, 66
p. 45
p. 29, 62
p. 42
p. 55
p. 43
p. 44, 64
p. 45
p. 46
p. 48
p. 65
p. 21
p. 37
p. 42, 43
p. 48, 52
p. 51, 68
p. 56
p. 67
C
M. Capdevila
F. Capitelli
M. A. M. Capozzi
C. Cardellicchio
6-7 June 2013, Milan, Italy
p. 17
p. 47
p. 47
p. 47
E. Cariati
M. Carini
L. Carlucci
L. Catalano
G. Cavallo
V. V. Chabukswar
F. Chiaravalotti
G. Ciani
A. Citterio
L. Colombo
A. Comotti
A. Crispini
D. Crocco
p. 50
p. 54
p. 33
p. 48
p. 39, 50, 56
p. 65
p. 54
p. 33
p. 65
p. 49, 53
p. 42, 43
p. 12, 54
p. 60, 66
D
S. D'Agostino
E. Dalcanale
F. De Marco
G. De Munno
V. Di Noto
V. Dichiarante
I. Ĉiloviü
R. E. Dinnebier
R. P. Doyle
p. 48
p. 21
p. 46
p. 58
p. 44
p. 50
p. 51, 68
p. 51, 55
p. 58
E
L. Erra
p. 62
F
G. A. Facey
F. Farinella
F. Fernandez-Palacio
V. Ferretti
A. Ferrise
A. Forni
p. 56
p. 52
p. 53
p. 13
p. 54
p. 50
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FROM SMALL MOLECULES TO MACROMOLECULES AND SUPRAMOLECULAR STRUCTURES
J. A. Foster
T. Frišþiü
K. Fucke
M. Fumanal
p. 59
p. 55
p. 59
p. 17
G
C. Gaeta
A. Gal
V. Gandin
G. Gattuso
M. Ghedini
G. Giffin
N. Godbert
F. Grepioni
D. Gur
p. 62
p. 26
p. 64
p. 61
p. 12, 54
p. 44
p. 12, 54
p. 28, 48
p. 26
H
I. Halasz
K. N. Hondore
V. Honkimäki
M. W. Hosseini
p. 51, 55, 68
p. 65
p. 55
p. 36
I
O. Ikkala
p. 32
K
S. P. Kelley
S. A. J. Kimber
Z. Kokan
6-7 June 2013, Milan, Italy
p. 62
M
L. Maini
M. Mališ
L. Marchio
N. Marino
J. Martí-Rujas
C. Marzano
M. Masino
C. Massera
P. P. Mazzeo
L. Meazza
K. Merz
P. Metrangolo
R. A. Michelin
J. S. Miller
K. C. Mohite
A. Monica
M. Mozzon
p. 52
p. 51
p. 42
p. 58
p. 53
p. 64
p. 60
p. 21, 67
p. 52
p. 59
p. 40
p. 39, 44, 49, 50, 53,
56, 59
p. 64
p. 17
p. 65
p. 60
p. 64
N
P. Neri
A. Notti
J. J. Novoa
p. 62
p. 61
p. 17
O
p. 11
p. 55
p. 51
L
M. La Deda
J. Lin
C. Loffi
M. Lusi
p. 12
p. 56
p. 57
L. Öhrström
p. 22
P
N. S. Pande
P. Paoli
S. Pappalardo
M. F. Parisi
P. Pelagatti
p. 65
p. 34
p. 61
p. 61
p. 23, 57, 63
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M. Piga
T. Pilati
R. Pinalli
D. M. Proserpio
D. Pucci
V. Purohit
A. Puškariü
p. 44
p. 39, 44, 49, 50, 53,
56, 61
p. 21
p. 33
p. 12
p. 65
p. 55
R
F. Rapaccioli
G. Resnati
S. M. Reutzel-Edens
A. G. Ricciardulli
K. Rissanen
R. D. Rogers
M. Rubþiü
p. 67
p. 39, 44, 49, 50, 53,
56, 59, 61
p. 27
p. 62
p. 20
p. 11
p. 51, 68
S
F. Sansone
F. Scè
A. Secchi
P. Sgarbossa
O. V. Shishkin
S. U. Shisodia
F. Silvestri
P. Sozzani
J. W. Steed.
R. S. Stein
6-7 June 2013, Milan, Italy
p. 45
p. 63
p. 67
p. 44, 64
p. 40
p. 65
p. 66
p. 42, 43
p. 59
p. 51
V. Štrukil
P. Swuec
p. 55
p. 57
T
C. Talotta
C. Tedesco
F. Terenziani
G. Terraneo
V. Tomišiü
I. Tosi
p. 62
p. 18, 62
p. 45
p. 39, 44, 49, 50, 53,
61
p. 51
p. 45
U
F. Ugozzoli
K. Užareviü
p. 21, 67
p. 51, 68
V
V. Vasylyeva
B. Ventura
p. 40
p. 48
W
S. Weiner
C. M. Widdifield
p. 26
p. 56
Z
M. J. Zaworotko
p. 16
76