The aromatic character of [10]annulenes and dicupra[10]annulenes from current density calculations

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Dimitrova , M & Sundholm , D 2018 , ' The aromatic character of [10]annulenes and dicupra[10]annulenes from current density calculations ' , Physical Chemistry Chemical Physics , vol. 20 , no. 3 , pp. 1337-1346 . https://doi.org/10.1039/c7cp07212k

Title: The aromatic character of [10]annulenes and dicupra[10]annulenes from current density calculations
Author: Dimitrova, Maria; Sundholm, Dage
Contributor organization: Department of Chemistry
Date: 2018-01-21
Language: eng
Number of pages: 10
Belongs to series: Physical Chemistry Chemical Physics
ISSN: 1463-9076
DOI: https://doi.org/10.1039/c7cp07212k
URI: http://hdl.handle.net/10138/309492
Abstract: We have investigated the aromatic properties of seven low-lying isomers of [10]annulene and of the recently synthesized dicupra[10]annulene compounds that were crystallised with two or four lithium counterions (Wei et al., J. Am. Chem. Soc., 2016, 138, 60-63). The molecular structures of the [10]annulene conformers and the dicupra[10]annulenes with bulky trimethylsilyl (TMS) and phenyl groups, as well as the corresponding unsubstituted dicupra[10]annulenes were optimised using density functional theory, employing a semiempirical dispersion correction to consider van der Waals interactions. The structures of the hydrocarbon annulenes were subsequently optimised at the SCS-MP2/def2-QZVPD level. Single-point coupled-cluster calculations with explicit treatment of the electron correlation CCSD(F12)(T) were performed to obtain the relative energies of the hydrocarbon annulenes. Four of the conformations lie close in energy relative to each other. Three substituted and three unsubstituted dicupra[10]annulene structures with either four, two or no Li+ counterions were investigated. Magnetically induced current densities calculated using the GIMIC program were used for the assessment of the aromatic properties of the studied molecules. The conformations of [10] annulene with lowest energies are non-aromatic. The calculations revealed that the electron donation of the lithium atoms to the dicupra[10]annulene core significantly affects the electronic and molecular structures of the dicupra[10]annulenes. The annulene ring is non-planar for all studied dicupra[10]annulenes except for the unsubstituted one with four Li+ counterions, which was also found to be the only molecule that sustains a strong diatropic ring current around the dicupra[10]annulene ring. The other five dicupra[10]annulenes sustain very weak net ring currents and can be considered non-aromatic.
Subject: 2ND-ORDER PERTURBATION-THEORY
INDEPENDENT CHEMICAL-SHIFTS
THE-IDENTITY APPROXIMATION
COUPLED-CLUSTER THEORY
ZETA VALENCE QUALITY
GAUSSIAN-BASIS SETS
RING CURRENTS
ELECTRON DELOCALIZATION
WORKSTATION COMPUTERS
COVALENT RADII
116 Chemical sciences
114 Physical sciences
Peer reviewed: Yes
Rights: unspecified
Usage restriction: openAccess
Self-archived version: acceptedVersion


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