Computational study of aromaticity, 1H NMR spectra and intermolecular interactions of twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives; Physical Chemistry Chemical Physics; Vol. 21, iss. 45

Computational study of aromaticity, 1H NMR spectra and intermolecular interactions of twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives; Physical Chemistry Chemical Physics; Vol. 21, iss. 45

Detalles Bibliográficos
Parent link:Physical Chemistry Chemical Physics
Vol. 21, iss. 45.— 2019.— [P. 25334-25343]
Autor Corporativo: Национальный исследовательский Томский политехнический университет Исследовательская школа химических и биомедицинских технологий
Outros autores: Baryshnikov G. V. Gleb Vladimirovich, Valiev R. R. Rashid Rinatovich, Li Qizhao, Li Chengjie, Xie Yongshu, Agren H. Hans
Summary:Title screen
The recently synthesized twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives have been studied computationally. Gauge-including magnetically induced current calculations predict a global nonaromatic character of the initial thia-norhexaphyrin due to the highly-twisted conformation of the macrocycle. Upon the oxidation of the thia-norhexaphyrin four multiply annulated polypyrrolic aromatic macrocycles are formed for which the global aromatic character is confirmed in agreement with experimentally measured 1H NMR spectra. The calculation of the proton chemical shifts for the studied compounds by direct comparison with the tetramethylsilane standard leads to a significant mean absolute error. At the same time a linear regression procedure for the two selected groups of protons (CH and NH protons) provides much better values of calculated chemical shifts and tight correlation with experiment. The separate consideration of NH protons is motivated by the numerous intermolecular hydrogen bonds in which the protons are involved, which induce considerable upfield shifts, leading to a significant underestimation of the corresponding chemical shifts. Such a selected correlation can be used for accurate estimation of proton chemical shifts of the related porphyrinoids. Bader's theory of Atoms in Molecules has been applied for the studied twisted thia-norhexaphyrin and its multiply annulated polypyrrolic derivatives to characterize intramolecular H-bonds and other non-covalent interactions.
Режим доступа: по договору с организацией-держателем ресурса
Idioma:inglés
Publicado: 2019
Subjects:
электронный ресурс
труды учёных ТПУ
Acceso en liña:http://dx.doi.org/10.1039/C9CP04819G
Formato: Electrónico Capítulo de libro
KOHA link:https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=661045

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