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ISSN 1998-9539

Supramolecular Regioselectivity of meso-Phenylporphyrin Sulfonation. Synthesis of 5,10,15-Tris(4’-sulfophenyl)porphine

Vladimir B. Sheinin,a@ Dmitriy A. Ivanov,a and Oscar I. Koifmana,b
Dedicated to Academician Aslan Yusupovich Tsivadze on the occasion of his Birthday
aG.A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences, 153045 Ivanovo, Russia
bIvanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia
@Corresponding author E-mail:
DOI: 10.6060/mhc170833s
Macroheterocycles 2017 10(4-5) 487-495
The results of the prognostic computer synthesis of meso-phenylporphyrins Н2Р(Ph)n sulfo derivatives, which demonstrate the supramolecular nature of the porphyrins sulfonation regioselectivity in concentrated sulfuric acid and oleum, are presented. By means of DFT calculation it has been shown that regioselectivityof meso-phenylporphyrins sulfonation is due to host-guest complex formation of the diprotonated porphyrin platform with two hydrosulfate anions, [H4P2+(Ph)n](HSO4-)2. The guest anions control the reactivity of H4P2+(Ph)n. First, they activate H4P2+(Ph)n for electrophilic substitution by partial negative charge transfer to the diprotonated porphyrin. Second, the guest anions are the cause of a total charges redistribution on the carbon atoms of H4P2+ and the phenyl rings, thereby providing the regioselectivity of H4P2+(Ph)n sulfonation. The data from prognostic stage calculations and method of organic synthesis were used to obtain the new 5,10,15-tris(4’-sulfophenyl)porphine. The obtained results are comprehensive and applicable to other SEAr reactions of porphyrins.


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