Optical and magnetic properties of antiaromatic porphyrinoids

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Valiev , R R , Fliegl , H & Sundholm , D 2017 , ' Optical and magnetic properties of antiaromatic porphyrinoids ' , Physical Chemistry Chemical Physics , vol. 19 , no. 38 , pp. 25979-25988 . https://doi.org/10.1039/c7cp05460b

Title: Optical and magnetic properties of antiaromatic porphyrinoids
Author: Valiev, Rashid R.; Fliegl, Heike; Sundholm, Dage
Contributor organization: Department of Chemistry
Date: 2017-10-14
Language: eng
Number of pages: 10
Belongs to series: Physical Chemistry Chemical Physics
ISSN: 1463-9076
DOI: https://doi.org/10.1039/c7cp05460b
URI: http://hdl.handle.net/10138/309500
Abstract: Magnetic and spectroscopic properties of a number of formally antiaromatic carbaporphyrins, carbathiaporphyrins and isophlorins with 4n pi 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 S-0 -> S-1 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 S-0 -> S-1 transition is a magnetic dipole-allowed electronic transition that is typical for antiaromatic porphyrinoids with 4n pi electrons.
Subject: DENSITY-FUNCTIONAL-THEORY
SENSITIZED SOLAR-CELLS
RING CURRENTS
AROMATIC PATHWAYS
COUPLED-CLUSTER
EXPANDED PORPHYRINS
CONJUGATION PATHWAYS
BASIS-SETS
SPECTROSCOPY
SYSTEMS
116 Chemical sciences
114 Physical sciences
Peer reviewed: Yes
Rights: unspecified
Usage restriction: openAccess
Self-archived version: acceptedVersion


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