Ion-molecular interactions in the metalloporphyrin-acid system in liquid solutions

• Published in: Journal of structural chemistry Vol. 55; no. 1; pp. 180 - 190
• Main Authors: Lomova, T. N., Klyueva, M. E., Mozhzhukhina, E. G., Tyulyaeva, E. Yu, Bichan, N. G., Zaitseva, S. V., Zdanovich, S. A.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 2014
• Subjects: 2012; Atomic; Atomic/Molecular Structure and Spectra; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Ivanovo; Molecular; Optical and Plasma Physics; Physical Chemistry; Proceedings of the 16th Symposium on Intermolecular Interactions and Conformations of Molecules June 18–22; Solid State Physics; associates; formation of H; porphyrins; properties; structure; complexes
• ISSN: 0022-4766; 1573-8779
• DOI: 10.1134/S0022476614010314

A new form of MP...H
solv
+
metalloporphyrins is found and studied in the strong acid medium, the conditions of its formation and the qualitative reaction of its determination are established. It is shown that the same form has the H
4
TPP
2+
dication (TPP is the 5,10,15,20-tetraphenyl-21H,23H-porphyrine dianion). The stability in different acid media and in the isolated state, spectral properties and the structure of H
+
-associates of porphyrins are analyzed in detail by UV-visible and
1
H NMR spectroscopy and quantum chemical calculations. It is shown that they have a unique two-band visible electronic spectrum with the bands near 540 nm and 700 nm, which weakly depend on the type of the central atom in the complex and noticeably change when the chromophore is functionally substituted. The proton location the ion-molecular associate and the cases of the formation of H
+
-associates with higher stoichiometry are revealed.