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Abstract:The mutual influence of ligands within the structure of Zn-porphyrins on the thermodynamic stability of the latter was investigated.

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meso -Arylporphyrins as most accessible tetrapyrrole macroheterocycles have always been the focus of attention from researchers concerned with practically useful properties of these compounds. The first syn­theses of meso -arylporphyrins date back to about 90 years ago. Up to now, the yields of these compounds have been improved from 5 to 80%. The present review analyzes different ways and strategies for the synthesis of meso -aryl-substituted porphyrins. The most efficient methods that can be scaled up to an industrial level have been identified.

Synthesis of bismuth complexes of etioporphyrin II, protoporphyrin IX dimethyl ester and three tetraphenylporphyrin derivatives in which iodine atom is an extraligand, was carried out. Obtained compounds were characterized by mass spectrometry, UV-vis, 1 H NMR spectroscopy, and HPLC. The study of X-ray spectra showed that bismuth valence is +3. Bismuth atom coordinates four nitrogen atoms and one iodine atom. All four nitrogen atoms Синтез и спектроскопические исследования порфиринатов висмута(III) иодидаКлючевые слова: Висмут, порфирин, металлокомплексы, ИК-спектроскопия, РФЭС, квантовохимические расчеты.The compounds were characterized by UV-vis, 1 H NMR spectroscopy, mass spectrometry and elemental analysis.Along with hydrophobic bismuth complexes, kinetically labile complexes with tetrasulfophenylporphyrin in an anion form and 5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin in a cation form were synthesized. [13] It is well-known that in its complexes bismuth has oxidation states +3 and +5, and its coordination number can vary from 3 to 10. Due to the large ionic radius of bismuth(III) 1.03 Å, it can not fit in porphyrin macrocycle plane, so bismuth is located above it. This fact leads to lability of bismuth-porphyrin complexes.The objective of the study reported here was to search for planar complexes with a strongly polarized «apix» metal-ligand bond -promising elements for a new electronic materials design. From this point of view bismuth(III) compounds with its spatially localized 6s 2 orbital are the perspective targets. The problem solution involves the synthesis of various Bi III I-porphyrins and their study by IR and X-ray spectroscopy methods, as well as analysis of porphyrin molecule spatial configuration influence on a possibility of complexation with bismuth iodide. Etioporphyrin II, whose bismuth(III) iodide complex thermal stability was studied previously, [14] protoporphyrin IX dimethyl ester (PP IX DME) (1) and three tetraphenylporphyrin derivatives (2-4) differ by substituents on phenyl rings and on macrocycle periphery, were selected as research objects (Figure 1).