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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

Selective Co-TPHAP− network formation.
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fig14: Selective Co-TPHAP− network formation.

Mentions: Reaction of K+·TPHAP− and CoII ions in a methanol/nitrobenzene solution generates several networks depending on temperature (Fig. 14 ▸). The reaction at 25°C generated thermally stable [Co(NO3−)(TPHAP−)(CH3OH)]·(solvent) (1), in which all TPHAP− anions function as tridentate ligands to form a two-dimensional layered structure. However, using the same starting materials and solvent, the reaction at 14°C generated a totally different porous network, [Co(TPHAP−)2(CH3OH)2(H2O)]·(solvent) (2), which is a kinetic product. The network structure 2 is formed by hydrogen bonds and π–π stacking of one-dimensional chains composed of CoII and both monodentate and bidentate TPHAP−. The CoII centre has octahedral geometry coordinated by two bidentate and one monodentate TPHAP−, two methanol molecules, and one water molecule. Within a few days after the crystal formation, the crystals of 2 started to shrink and new dark-red crystals grew on the crystal surface. Synchrotron single-crystal X-ray analysis revealed that those crystals are uniform and the crystal structure is the coordination network, [Co(NO3−)(TPHAP−)(CH3OH)2]·(solvent) (3), com­posed of one-dimensional chains of CoII and bidentate TPHAP−. During the crystal transformation, monodentate TPHAP− and water around CoII in 2 were exchanged with bidentate NO3− to produce 3. Crystal 3 showed no further transformation, indicating that 3 is thermodynamically more stable than 2. Of note is that 3 can be prepared by structural transformation of 2, but not through 1. This illustrates that some materials can be prepared only via kinetic states rather than through thermodynamic experimental conditions.


Supramolecular interactions in the solid state.

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

Selective Co-TPHAP− network formation.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig14: Selective Co-TPHAP− network formation.
Mentions: Reaction of K+·TPHAP− and CoII ions in a methanol/nitrobenzene solution generates several networks depending on temperature (Fig. 14 ▸). The reaction at 25°C generated thermally stable [Co(NO3−)(TPHAP−)(CH3OH)]·(solvent) (1), in which all TPHAP− anions function as tridentate ligands to form a two-dimensional layered structure. However, using the same starting materials and solvent, the reaction at 14°C generated a totally different porous network, [Co(TPHAP−)2(CH3OH)2(H2O)]·(solvent) (2), which is a kinetic product. The network structure 2 is formed by hydrogen bonds and π–π stacking of one-dimensional chains composed of CoII and both monodentate and bidentate TPHAP−. The CoII centre has octahedral geometry coordinated by two bidentate and one monodentate TPHAP−, two methanol molecules, and one water molecule. Within a few days after the crystal formation, the crystals of 2 started to shrink and new dark-red crystals grew on the crystal surface. Synchrotron single-crystal X-ray analysis revealed that those crystals are uniform and the crystal structure is the coordination network, [Co(NO3−)(TPHAP−)(CH3OH)2]·(solvent) (3), com­posed of one-dimensional chains of CoII and bidentate TPHAP−. During the crystal transformation, monodentate TPHAP− and water around CoII in 2 were exchanged with bidentate NO3− to produce 3. Crystal 3 showed no further transformation, indicating that 3 is thermodynamically more stable than 2. Of note is that 3 can be prepared by structural transformation of 2, but not through 1. This illustrates that some materials can be prepared only via kinetic states rather than through thermodynamic experimental conditions.

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