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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

Crystalline-to-amorphous-to-crystalline network transformation.
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fig16: Crystalline-to-amorphous-to-crystalline network transformation.

Mentions: As mentioned above, some materials can be prepared only through a kinetic intermediate by controlling the reaction conditions (Ohara et al., 2009 ▸). The thermodynamic stability of a network is important for industrial applications. For example, a metastable interpenetrating network, [(ZnI2)3(TPT)2]·(solvent) (Biradha & Fujita, 2002 ▸), can be prepared as a fine powder by instant synthesis from ZnI2 and TPT in nitrobenzene/methanol. When the powder of the interpenetrating network is heated, an amorphous phase is generated at 200°C. Surprisingly, further heating at 300°C generates a new crystalline phase which is a saddle type of porous network (Fig. 16 ▸). The crystal structure was solved ab initio from XRPD data. The saddle structure is remarkably stable up to 400°C. It is noteworthy that it cannot be prepared by grinding and heating a mixed powder of ZnI2 and TPT. The fact that it is generated only via the interpenetrating structure indicates that preorganization of ZnI2 and TPT is essential.


Supramolecular interactions in the solid state.

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

Crystalline-to-amorphous-to-crystalline network transformation.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig16: Crystalline-to-amorphous-to-crystalline network transformation.
Mentions: As mentioned above, some materials can be prepared only through a kinetic intermediate by controlling the reaction conditions (Ohara et al., 2009 ▸). The thermodynamic stability of a network is important for industrial applications. For example, a metastable interpenetrating network, [(ZnI2)3(TPT)2]·(solvent) (Biradha & Fujita, 2002 ▸), can be prepared as a fine powder by instant synthesis from ZnI2 and TPT in nitrobenzene/methanol. When the powder of the interpenetrating network is heated, an amorphous phase is generated at 200°C. Surprisingly, further heating at 300°C generates a new crystalline phase which is a saddle type of porous network (Fig. 16 ▸). The crystal structure was solved ab initio from XRPD data. The saddle structure is remarkably stable up to 400°C. It is noteworthy that it cannot be prepared by grinding and heating a mixed powder of ZnI2 and TPT. The fact that it is generated only via the interpenetrating structure indicates that preorganization of ZnI2 and TPT is essential.

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