New insights into aromatic pathways of carbachlorins and carbaporphyrins based on calculations of magnetically induced current densities

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http://hdl.handle.net/10138/224398

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Benkyi , I , Fliegl , H , Valiev , R R & Sundholm , D 2016 , ' New insights into aromatic pathways of carbachlorins and carbaporphyrins based on calculations of magnetically induced current densities ' , Physical Chemistry Chemical Physics , vol. 18 , no. 17 , pp. 11932-11941 . https://doi.org/10.1039/c5cp06987d

Title: New insights into aromatic pathways of carbachlorins and carbaporphyrins based on calculations of magnetically induced current densities
Author: Benkyi, Isaac; Fliegl, Heike; Valiev, Rashid R.; Sundholm, Dage
Contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Laboratory for Instruction in Swedish (-2016)
Date: 2016-05-02
Language: eng
Number of pages: 10
Belongs to series: Physical Chemistry Chemical Physics
ISSN: 1463-9076
URI: http://hdl.handle.net/10138/224398
Abstract: Magnetically induced current densities have been calculated and analyzed for a number of synthesized carbachlorins and carbaporphyrins using density functional theory and the gauge including magnetically induced current (GIMIC) method. Aromatic properties have been determined by using accurate numerical integration of the current flow yielding reliable current strengths and pathways that are related to the degree of aromaticity and the aromatic character of the studied molecules. All investigated compounds are found to be aromatic. However, the obtained aromatic pathways differ from those previously deduced from spectroscopic data and magnetic shielding calculations. For all studied compounds, the ring current divides into an outer and an inner branch at each pyrrolic subring, showing that all pi-electrons of the pyrrolic rings take part in the delocalization pathway. The calculations do not support the common notion that the main share of the current takes the inner route at the pyrrolic rings without an inner hydrogen and follows an 18 pi aromatic pathway. The aromatic pathways of the investigated carbaporphyrins and carbachlorins are very similar, since the current strength via the C-beta=C-beta' bond of the cyclopentadienyl ring of the carbaporphyrins is almost as weak as the current density passing the corresponding saturated C beta-C-beta' bond of the carbachlorins.
Subject: INDEPENDENT CHEMICAL-SHIFTS
RING CURRENTS
STRUCTURAL-CHARACTERIZATION
WORKSTATION COMPUTERS
PERTURBATION-THEORY
CURRENT MODEL
BASIS-SETS
PORPHYRINS
NICS
DELOCALIZATION
116 Chemical sciences
114 Physical sciences
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