Chemistry, Physics and Technology of Surface

ISSN 2518-1238 (Online), ISSN 2079-1704 (Print)

The paper deals with a relatively new type of three-dimensional sorbents that are called metal-organic frameworks. The chemical compounds of this kind can be regarded as crystal sponges since they are microporous solid phases with exclusively large area of accessible internal surface. The most expressive manifestation of the peculiarity of the metal-organic frameworks is the topological equivalence of the metal-organic frameworks with principally different chemical nature. This phenomenon is sometimes called an isoreticular paradox.

Such sorbents possess an exclusive identity of pores which is provided by the crystalline order in their structures. In its turn the crystalline order of the structure imposes severe restrictions on the geometry and topology of cavities in the structure frame and on the spatial symmetry of the structure itself. Revealing the characteristic features of structure forming in metal-organic coordination polymers enabled to estimate the relative frequencies of possible spatial structures of metal-organic frameworks. The isoreticular paradox originates from the finite number of formally possible Fedorov groups being aggravated by the sharply uneven distribution of the probabilities of these groups in real crystal structures.

An atomic configuration of a frame cavity is isomorphic to a concave polyhedron. The symmetry of such polyhedra is to comply with the crystal lattice. We have found eleven Hessel groups that correspond to possible cavity polyhedral and estimated the relative probabilities of cavity configurations in the frame structures. The structural design of framework sorbents should provide the topologic combinations of atomic complexes and molecular linkers providing the cavity configurations of the above mentioned eleven types and forming the centrosymmetric spatial structure.

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