Журнал "Макрогетероциклы"

Dmitriy A. Ivanov,^a Vladimir B. Sheinin,^а@ Alexey V. Lyubimtsev,^b Olga M. Kulikova,^a and Oscar I. Koifman^a,b

^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: vbs@isc-ras.ru

DOI: 10.6060/mhc190338s

Macroheterocycles 2019 12(4) 375-381

Water-soluble 5-(4`-aminophenyl)-10,15,20-tris(4`-sulfophenyl)porphine was obtained by three-stage synthesis from tetraphenylporphyrin under conditions of supramolecular control of regioselectivity of nitration and sulfonation reactions. In acidic medium (pH ≈ 2) the trianion H₂P(PhNH₂)(PhSO₃^–)₃ is protonated at the porphyrin platform and the amino group to form the aqua complex of the zwitterion [H₄P²⁺(PhNH₃)(PhSO₃H)(PhSO₃^–)₂](H₂O)₂, which is self-assembled into porphyrin nanotubes (PNTs), the outer surface of which is covered with positively charged groups -PhNH₃⁺, and the inner surface with electroneutral groups -PhSO₃H. By the action of nitrous acid, stable diazotized PNTs were obtained. Supramolecular self-assembly inhibits the azo coupling reaction of H₄P²⁺(PhN₂⁺)(PhSO₃H)(PhSO₃^–)₂ tectons with H-acid in an acidic medium. H-Conjugate was obtained by azo coupling in an alkaline medium (pH ≈ 10), where diazotized PNTs are destroyed with formation of the diazocompound H₂P(PhN₂⁺)(PhSO₃^–)₃. The resulting product was characterized by ¹H NMR, MS MALDI-TOF and UV-Vis spectra.