Optical and magnetic properties of antiaromatic porphyrinoids; Physical Chemistry Chemical Physics; Vol. 19, iss. 38

Optical and magnetic properties of antiaromatic porphyrinoids; Physical Chemistry Chemical Physics; Vol. 19, iss. 38

Bibliographic Details
Parent link:Physical Chemistry Chemical Physics
Vol. 19, iss. 38.— 2017.— [P. 25979-25988]
Main Author: Valiev R. R. Rashid Rinatovich
Corporate Author: Национальный исследовательский Томский политехнический университет (ТПУ) Институт физики высоких технологий (ИФВТ) Кафедра общей химии и химической технологии (ОХХТ)
Other Authors: Fliegl H. Heike, Sundholm D. Dage
Summary:Title screen
Magnetic and spectroscopic properties of a number of formally antiaromatic carbaporphyrins, carbathiaporphyrins and isophlorins with 4n ? electrons have been investigated at density functional theory and ab initio levels of theory. The calculations show that the paratropic contribution to the magnetically induced ring-current strength susceptibility and the magnetic dipole-transition moment between the ground and the lowest excited state are related. The vertical excitation energy (VEE) of the first excited state decreases with increasing ring-current strength susceptibility, whereas the VEE of the studied higher-lying excited states are almost independent of the size of the ring-current strength susceptibility. Strong antiaromatic porphyrinoids, based on the magnitude of the paratropic ring-current strength susceptibility, have small energy gaps between the highest occupied and lowest unoccupied molecular orbitals and a small VEE of the first excited state. The calculations show that only the lowest S0 > S1 transition contributes signficantly to the magnetically induced ring-current strength susceptibility of the antiaromatic porphyrinoids. The decreasing optical gap combined with a large angular momentum contribution to the magnetic transition moment from the first excited state explains why molecules III–VII are antiaromatic with very strong paratropic ring-current strength susceptibilities. The S0 > S1 transition is a magnetic dipole-allowed electronic transition that is typical for antiaromatic porphyrinoids with 4n ? electrons.
Режим доступа: по договору с организацией-держателем ресурса
Language:English
Published: 2017
Subjects:
электронный ресурс
труды учёных ТПУ
Online Access:http://dx.doi.org/10.1039/C7CP05460B
Format: Electronic Book Chapter
KOHA link:https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=656154

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