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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

Halogen-bonded adducts formed by the tetradentate XB acceptor tetra-4-pyridyl-pentaerythritol. (a) Two-dimensional square grid formed with the bidentate XB donor 1,6-diiodoperfluorohexane; (b) three-dimensional adamantanoid network formed with the bidentate XB donor 1,4-diiodoperfluorobutane (Metrangolo et al., 2007 ▸). H atoms are omitted. XBs are shown as black dotted lines. XB separations, angles and colour codes are as in Fig. 1 ▸.
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fig2: Halogen-bonded adducts formed by the tetradentate XB acceptor tetra-4-pyridyl-pentaerythritol. (a) Two-dimensional square grid formed with the bidentate XB donor 1,6-diiodoperfluorohexane; (b) three-dimensional adamantanoid network formed with the bidentate XB donor 1,4-diiodoperfluorobutane (Metrangolo et al., 2007 ▸). H atoms are omitted. XBs are shown as black dotted lines. XB separations, angles and colour codes are as in Fig. 1 ▸.

Mentions: Preparation of the I2⋯NH3 adduct was described as early as 200 years ago (Colin, 1814 ▸), but the potential of halogen atoms to drive recognition phenomena and self-assembly processes long remained unrecognized. The general and manifold ability of halogen atoms to be involved in attractive interactions was acknowledged only in the late 1990s when it was observed that metal-bound Cl often accepts hydrogen bonds (Aullón et al., 1998 ▸) and that the I atom of iodoperfluorocarbons gives quite strong interactions with atoms possessing lone pairs (Metrangolo & Resnati, 2001 ▸; Figs. 1 ▸ and 2 ▸) or with anions (Cavallo et al., 2010 ▸; Fig. 3 ▸). This latter type of interaction, where the halogen atom acts as an electrophile (as in the I2⋯NH3 adduct mentioned above), has now become a valuable tool in crystal engineering. According to a recent IUPAC recommendation, these interactions are named halogen bonds (Desiraju et al., 2013 ▸). Specifically: ‘A halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity’. Throughout this article, the acronym XB will be used to denote halogen bond.


Supramolecular interactions in the solid state.

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

Halogen-bonded adducts formed by the tetradentate XB acceptor tetra-4-pyridyl-pentaerythritol. (a) Two-dimensional square grid formed with the bidentate XB donor 1,6-diiodoperfluorohexane; (b) three-dimensional adamantanoid network formed with the bidentate XB donor 1,4-diiodoperfluorobutane (Metrangolo et al., 2007 ▸). H atoms are omitted. XBs are shown as black dotted lines. XB separations, angles and colour codes are as in Fig. 1 ▸.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig2: Halogen-bonded adducts formed by the tetradentate XB acceptor tetra-4-pyridyl-pentaerythritol. (a) Two-dimensional square grid formed with the bidentate XB donor 1,6-diiodoperfluorohexane; (b) three-dimensional adamantanoid network formed with the bidentate XB donor 1,4-diiodoperfluorobutane (Metrangolo et al., 2007 ▸). H atoms are omitted. XBs are shown as black dotted lines. XB separations, angles and colour codes are as in Fig. 1 ▸.
Mentions: Preparation of the I2⋯NH3 adduct was described as early as 200 years ago (Colin, 1814 ▸), but the potential of halogen atoms to drive recognition phenomena and self-assembly processes long remained unrecognized. The general and manifold ability of halogen atoms to be involved in attractive interactions was acknowledged only in the late 1990s when it was observed that metal-bound Cl often accepts hydrogen bonds (Aullón et al., 1998 ▸) and that the I atom of iodoperfluorocarbons gives quite strong interactions with atoms possessing lone pairs (Metrangolo & Resnati, 2001 ▸; Figs. 1 ▸ and 2 ▸) or with anions (Cavallo et al., 2010 ▸; Fig. 3 ▸). This latter type of interaction, where the halogen atom acts as an electrophile (as in the I2⋯NH3 adduct mentioned above), has now become a valuable tool in crystal engineering. According to a recent IUPAC recommendation, these interactions are named halogen bonds (Desiraju et al., 2013 ▸). Specifically: ‘A halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity’. Throughout this article, the acronym XB will be used to denote halogen bond.

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