Aromaticity of the doubly charged [8]circulenes

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Baryshnikov , G V , Valiev , R R , Karaush , N N , Sundholm , D & Minaev , B F 2016 , ' Aromaticity of the doubly charged [8]circulenes ' , Physical Chemistry Chemical Physics , vol. 18 , no. 13 , pp. 8980-8992 . https://doi.org/10.1039/c6cp00365f

Title: Aromaticity of the doubly charged [8]circulenes
Author: Baryshnikov, Gleb V.; Valiev, Rashid R.; Karaush, Nataliya N.; Sundholm, Dage; Minaev, Boris F.
Contributor: University of Helsinki, Department of Chemistry
Date: 2016-04-07
Language: eng
Number of pages: 13
Belongs to series: Physical Chemistry Chemical Physics
ISSN: 1463-9076
URI: http://hdl.handle.net/10138/224362
Abstract: Magnetically induced current densities and current pathways have been calculated for a series of fully annelated dicationic and dianionic tetraphenylenes, which are also named [8]circulenes. The gauge including magnetically induced current (GIMIC) method has been employed for calculating the current density susceptibilities. The aromatic character and current pathways are deduced from the calculated current density susceptibilities showing that the neutral [8]circulenes have two concentric pathways with aromatic and antiaromatic character, respectively. The inner octatetraene core (the hub) is found to sustain a paratropic (antiaromatic) ring current, whereas the ring current along the outer part of the macrocycle (the rim) is diatropic (aromatic). The neutral [8]circulenes can be considered nonaromatic, because the sum of the ring-current strengths of the hub and the rim almost vanishes. The aromatic character of the doubly charged [8]circulenes is completely different: the dianionic [8]circulenes and the OC-, CH-, CH2-, SiH-, GeH-, SiH2-, and GeH2-containing dicationic species sustain net diatropic ring currents i.e., they are aromatic, whereas the O-, S-, Se-, NH-, PH- and AsH-containing dicationic [8]circulenes are strongly antiaromatic. The present study also shows that GIMIC calculations on the [8]circulenes provide more accurate information about the aromatic character than that obtained using local indices such as nuclear-independent chemical shifts (NICSs) and H-1 NMR chemical shifts.
Subject: INDEPENDENT CHEMICAL-SHIFTS
MAGNETICALLY INDUCED CURRENTS
TRANSITION-METAL CLUSTERS
INDUCED CURRENT DENSITIES
ELECTRONIC-STRUCTURE
RING CURRENT
ORGANIC SEMICONDUCTORS
GIMIC CHARACTERIZATION
NICS
MOLECULES
116 Chemical sciences
114 Physical sciences
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