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Journal of Structural Chemistry

2014 year, number 5

STRUCTURE OF PORPHYRIN H-ASSOCIATES, INVERTED PORPHYRINOIDS, AND CORROLES WITH N,N-DIMETHYLFORMAMIDE

D. B. Berezin1, M. A. Krest'yaninov2
1Ivanovo State University of Chemical Technology, Ivanovo, Russia
2Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: porphyrin, porphyrinoid, corrole, inverted porphyrin isomer, N,N-dimethylformamide, Н-associate, intramolecular hydrogen bond, chemical activity of the NH bond, geometry optimization, NBO analysis

Abstract

By means of quantum-chemical calculations (DFT B3LYP, CC-pVDZ basis set) the previously proposed structure and interaction energy of the components of H-associates of meso -tetraphenylporphyrin and its analogues (comp. I-III) with N,N-dimethylformamide (DMF) of the 1:1 composition is confirmed theoretically for the first time. In the ability to form H-associates involving NH bonds of intramolecular coordination centers (CCs) the macrocycles can be ordered as: IIII b < III a < II. Tautomer III b is shown to form an Н-associate involving an outer-cyclic 2NH proton, and a macrocycle of corrole II has a strong intramolecular H bond in CC. One of the factors determining the NH activity of macrocycles is the degree of a deviation of the intracyclic NH protons from the plane of the molecule in its non-associated form.