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Supramolecular interactions in the solid state.

Resnati G, Boldyreva E, Bombicz P, Kawano M - IUCrJ (2015)

Bottom Line: In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond.Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena.The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

View Article: PubMed Central - HTML - PubMed

Affiliation: Department of Chemistry, Materials, Chemical Engineering, Politecnico di Milano , 7, via Mancinelli, Milan, Lombardy I-20131, Italy.

ABSTRACT
In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1) an overview and historical review of halogen bonding; (2) exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3) the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4) strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

No MeSH data available.


Related in: MedlinePlus

Synthon engineering: directed manipulation of the packing arrangement through supramolecular interactions. Examples from a series of laterally disubstituted calixarenes (Fischer et al., 2012 ▸, 2013 ▸). The main packing motif in all structures is a molecular chain, irrespective of the size and chemical functionality of the lateral substituents, or the different space groups. The structural properties are sensitively tuned by application of secondary interactions governed by the fine balance of spatial and electrostatic forces.
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fig11: Synthon engineering: directed manipulation of the packing arrangement through supramolecular interactions. Examples from a series of laterally disubstituted calixarenes (Fischer et al., 2012 ▸, 2013 ▸). The main packing motif in all structures is a molecular chain, irrespective of the size and chemical functionality of the lateral substituents, or the different space groups. The structural properties are sensitively tuned by application of secondary interactions governed by the fine balance of spatial and electrostatic forces.

Mentions: The total space available for the guest molecules expands by the introduction of a lateral substituent to the calixarene molecule. The guest molecules are positioned interstitially as the cone conformation of the calixarene changes to a ‘partial cone’ by the effect of the bridge monosubstitution. The lateral attachment acts as a spacer, which at the same time reduces the close packing of the crystal due to increased asymmetry of the calixarene chalice. Influenced by the supramolecular interactions and the steric demands of the substituent, the serpentine-like channels observed in the unsubstituted calixarene structure are straightened to linear in the mono-substituted case (Fischer et al., 2011 ▸). Introduction of a second substituent on the opposite methylene unit of the calix[4]arene exercises a distinct influence both on the host conformation and on the supramolecular architecture (Fig. 11 ▸). The partial cone transforms to a 1,2-alternate conformation and the two lateral attachments enforce a staggered arrangement of the calixarene molecules. This packing motif, a molecular chain along the axis of the bridge substitution, can be very sensitively tuned by the size and functionality of the substituents. The principal motif of the molecular column remains in the structures, irrespective of the size and functionality of the lateral substituents and the crystal system or space group. Nevertheless, the supramolecular synthon within the molecular chain might be tuned by the fine balance of the spatial and electrostatic forces (Fig. 11 ▸). The columnar packing motif appears even without guest molecules in the case of appropriately selected lateral substituents (Fischer et al., 2012 ▸), and the chain is assembled irrespective of the polar or nonpolar character of the bridge substituent. If a size limit is exceeded, the lateral substituent takes part in the supramolecular bonding pattern. Keeping the robust common columnar packing motif, the crystal packing transforms from one pattern into another by translation and rotation in the different crystal structures. These calix[4]arene inclusion compounds are excellent examples of morphotropy induced by supramolecular interactions. The mastering of the supramolecular packing architecture, e.g. directed manipulation of molecular packing arrangement via the supramolecular interactions, can be appropriately described as synthon engineering (Bombicz et al., 2014 ▸).


Supramolecular interactions in the solid state.

Resnati G, Boldyreva E, Bombicz P, Kawano M - IUCrJ (2015)

Synthon engineering: directed manipulation of the packing arrangement through supramolecular interactions. Examples from a series of laterally disubstituted calixarenes (Fischer et al., 2012 ▸, 2013 ▸). The main packing motif in all structures is a molecular chain, irrespective of the size and chemical functionality of the lateral substituents, or the different space groups. The structural properties are sensitively tuned by application of secondary interactions governed by the fine balance of spatial and electrostatic forces.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4645112&req=5

fig11: Synthon engineering: directed manipulation of the packing arrangement through supramolecular interactions. Examples from a series of laterally disubstituted calixarenes (Fischer et al., 2012 ▸, 2013 ▸). The main packing motif in all structures is a molecular chain, irrespective of the size and chemical functionality of the lateral substituents, or the different space groups. The structural properties are sensitively tuned by application of secondary interactions governed by the fine balance of spatial and electrostatic forces.
Mentions: The total space available for the guest molecules expands by the introduction of a lateral substituent to the calixarene molecule. The guest molecules are positioned interstitially as the cone conformation of the calixarene changes to a ‘partial cone’ by the effect of the bridge monosubstitution. The lateral attachment acts as a spacer, which at the same time reduces the close packing of the crystal due to increased asymmetry of the calixarene chalice. Influenced by the supramolecular interactions and the steric demands of the substituent, the serpentine-like channels observed in the unsubstituted calixarene structure are straightened to linear in the mono-substituted case (Fischer et al., 2011 ▸). Introduction of a second substituent on the opposite methylene unit of the calix[4]arene exercises a distinct influence both on the host conformation and on the supramolecular architecture (Fig. 11 ▸). The partial cone transforms to a 1,2-alternate conformation and the two lateral attachments enforce a staggered arrangement of the calixarene molecules. This packing motif, a molecular chain along the axis of the bridge substitution, can be very sensitively tuned by the size and functionality of the substituents. The principal motif of the molecular column remains in the structures, irrespective of the size and functionality of the lateral substituents and the crystal system or space group. Nevertheless, the supramolecular synthon within the molecular chain might be tuned by the fine balance of the spatial and electrostatic forces (Fig. 11 ▸). The columnar packing motif appears even without guest molecules in the case of appropriately selected lateral substituents (Fischer et al., 2012 ▸), and the chain is assembled irrespective of the polar or nonpolar character of the bridge substituent. If a size limit is exceeded, the lateral substituent takes part in the supramolecular bonding pattern. Keeping the robust common columnar packing motif, the crystal packing transforms from one pattern into another by translation and rotation in the different crystal structures. These calix[4]arene inclusion compounds are excellent examples of morphotropy induced by supramolecular interactions. The mastering of the supramolecular packing architecture, e.g. directed manipulation of molecular packing arrangement via the supramolecular interactions, can be appropriately described as synthon engineering (Bombicz et al., 2014 ▸).

Bottom Line: In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond.Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena.The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

View Article: PubMed Central - HTML - PubMed

Affiliation: Department of Chemistry, Materials, Chemical Engineering, Politecnico di Milano , 7, via Mancinelli, Milan, Lombardy I-20131, Italy.

ABSTRACT
In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1) an overview and historical review of halogen bonding; (2) exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3) the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4) strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

No MeSH data available.


Related in: MedlinePlus