Structural supramolecular chemistry
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2020-06-09 14:01
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LIPKOWSKI, Janusz. Structural supramolecular chemistry. In: The International Conference dedicated to the 55th anniversary from the foundation of the Institute of Chemistry of the Academy of Sciences of Moldova, 28-30 mai 2014, Chișinău. Chișinău, Republica Moldova: Institutul de Chimie al AȘM, 2014, p. 11.
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The International Conference dedicated to the 55th anniversary from the foundation of the Institute of Chemistry of the Academy of Sciences of Moldova 2014
Conferința "The International Conference dedicated to the 55th anniversary from the foundation of the Institute of Chemistry of the Academy of Sciences of Moldova"
Chișinău, Moldova, 28-30 mai 2014

Structural supramolecular chemistry


Pag. 11-11

Lipkowski Janusz
 
Cardinal Stefan Wyszyński University in Warsaw
 
 
Disponibil în IBN: 18 ianuarie 2019


Rezumat

'Supramolecular' means combination of molecular species without formation of covalent bonds between the components. Structural crystallography is the ideal experimental technique to study the structure of supramolecular complexes since it is very little, if any, sensitive to the noncrystalline environment of the investigated samples. Topological bonding in chemistry, essential in supramolecular systems, has very long history dating back to first synthesis of organic compound (Wőhler) or discovery of chlorine (Scheele). Both were prepared in the form of solvates but it was in 1948 only when the nature of non-covalent bonding between the components was described based on x-ray structural work (Powell). Cyclodextrins are commonly known as materials having intra-molecular cavity able to accommodate guest species. This property, when combined with sorption in the inter-molecular space in the solid state structures of CDs leads to very interesting structures and properties. In general, such behavior may be observed only when CD moieties are at equilibrium with a solution of the respective guest and solvent species. The equilibria are quite sensitive to minor changes of solution chemical composition what may be observed microscopically as morphology changes of the crystalline phases. This phenomenon will be illustrated with short movies demonstrating crystal behavior on change of its environment. Novel x-ray structures will also be demonstrated. The phenomenon of lattice dilation/contraction is characteristic for an ‘organic zeolite’ type structure which is one of the cyclodextrin structural type recently found in our studies. Hydrophobic hydration is the concept derived in the 1950s from thermodynamic studies from which it became clear that, in addition to hydrogen bonding, water has some extra ability to bind, without hydrophilic interactions, molecular species which are routinely considered hydrophobic. The outcome, e.g. in the form of stable compounds of water and hydrocarbons, is impressive. This binding is based upon structure effects, namely on aggregation of water molecules around a ‘structure-directing agent’ (as named by silica chemists) or ‘template’ (commonly used by organic synthetic chemists) or, simply, guest component. This is a typical collective phenomenon, not easily corresponding to the classical tools of chemists who prefer to rationalize interactions in terms of bonds between specified atoms. Hydrate solids are often nonstoichiometric, phenomenon which is certainly unknown in molecular chemistry while rather common in solid state sciences. Solid state inclusion compounds are, from the physicochemical standpoint, interstitial solid solutions of the guest in the metastable host scaffold. There is a certain minimum guest/host filling ratio at which the structure is thermodynamically stable, the full occupancy being the upper limit of the guest/host ratio. Hydrophobic hydration/solvation is a general phenomenon, the examples in the paper may serve as the experimental prove of it.