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π-Electron ring currents and magnetic properties of porphyrin molecules in the MO LCAO SCF method

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Abstract

The coupled variant of double-parameter perturbation theory in the MO LCAO SCF method in the London approximation has been used for the calculation of π-electron current distributions in the molecules of porphin and its derivatives. The chemical shifts of1H-NMR have been computed on the basis of calculations of ring currents and charge distributions. It is shown that π-electron ring currents are responsible for the dominant contribution to the shielding of protons. The theoretical and experimental values of proton chemical shifts are in a good agreement. Chemical shifts of the13C and15N nuclei have also been estimated. Two aromaticity scales are proposed for the compounds under study based on the calculations of the π-electron contribution to the diamagnetic susceptibility and of π-electron currents, respectively.

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Authors and Affiliations

  1. Institute of Physicoorganic Chemistry and Coal Chemistry, Academy of Sciences of the Ukrainian SSR, R. Luxemburg Street 70, 340048, Donetsk, USSR

    Yuri B. Vysotsky

  2. Institute of Physics, Academy of Sciences of the Byelorussian SSR, Leninsky Prospekt 70, 220072, Minsk, USSR

    Valery A. Kuzmitsky & Konstantin N. Solovyov

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  1. Yuri B. Vysotsky
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  2. Valery A. Kuzmitsky
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  3. Konstantin N. Solovyov
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Vysotsky, Y.B., Kuzmitsky, V.A. & Solovyov, K.N. π-Electron ring currents and magnetic properties of porphyrin molecules in the MO LCAO SCF method. Theoret. Chim. Acta 59, 467–485 (1981). https://doi.org/10.1007/BF02394651

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