Analysis of the magnetically induced current density of molecules consisting of annelated aromatic and antiaromatic hydrocarbon rings

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dc.contributor.author Sundholm, Dage
dc.contributor.author Berger, Raphael J. F.
dc.contributor.author Fliegl, Heike
dc.date.accessioned 2017-09-20T10:52:00Z
dc.date.available 2017-09-20T10:52:00Z
dc.date.issued 2016-06-21
dc.identifier.citation Sundholm , D , Berger , R J F & Fliegl , H 2016 , ' Analysis of the magnetically induced current density of molecules consisting of annelated aromatic and antiaromatic hydrocarbon rings ' , Physical Chemistry Chemical Physics , vol. 18 , no. 23 , pp. 15934-15942 . https://doi.org/10.1039/c6cp01968d
dc.identifier.other PURE: 67060343
dc.identifier.other PURE UUID: dba50e90-070d-492d-bd55-92f261bdb16a
dc.identifier.other WOS: 000378243000056
dc.identifier.other Scopus: 84973638069
dc.identifier.other ORCID: /0000-0002-2367-9277/work/28864310
dc.identifier.uri http://hdl.handle.net/10138/224360
dc.description.abstract Magnetically induced current susceptibilities and current pathways have been calculated for molecules consisting of two pentalene groups annelated with a benzene (1) or naphthalene (2) moiety. Current strength susceptibilities have been obtained by numerically integrating separately the diatropic and paratropic contributions to the current flow passing planes through chosen bonds of the molecules. The current density calculations provide novel and unambiguous current pathways for the unusual molecules with annelated aromatic and antiaromatic hydrocarbon moieties. The calculations show that the benzene and naphthalene moieties annelated with two pentalene units as in molecules 1 and 2, respectively, are unexpectedly antiaromatic sustaining only a local paratropic ring current around the ring, whereas a weak diatropic current flows around the C-H moiety of the benzene ring. For 1 and 2, the individual five-membered rings of the pentalenes are antiaromatic and a slightly weaker semilocal paratropic current flows around the two pentalene rings. Molecules 1 and 2 do not sustain any net global ring current. The naphthalene moiety of the molecule consisting of a naphthalene annelated with two pentalene units (3) does not sustain any strong ring current that is typical for naphthalene. Instead, half of the diatropic current passing the naphthalene moiety forms a zig-zag pattern along the C-C bonds of the naphthalene moiety that are not shared with the pentalene moieties and one third of the current continues around the whole molecule partially cancelling the very strong paratropic semilocal ring current of the pentalenes. For molecule 3, the pentalene moieties and the individual five-membered rings of the pentalenes are more antiaromatic than for 1 and 2. The calculated current patterns elucidate why the compounds with formally [4n + 2] p-electrons have unusual aromatic properties violating the Huckel pi-electron count rule. The current density calculations also provide valuable information for interpreting the measured H-1 NMR spectra. en
dc.format.extent 9
dc.language.iso eng
dc.relation.ispartof Physical Chemistry Chemical Physics
dc.rights cc_by_nc
dc.rights.uri info:eu-repo/semantics/openAccess
dc.subject INDEPENDENT CHEMICAL-SHIFTS
dc.subject INCLUDING ATOMIC ORBITALS
dc.subject CURRENT MODEL
dc.subject WORKSTATION COMPUTERS
dc.subject PERTURBATION-THEORY
dc.subject GLOBAL-MINIMUM
dc.subject PI-SYSTEMS
dc.subject BASIS-SETS
dc.subject ENERGY
dc.subject NAPHTHALENE
dc.subject 116 Chemical sciences
dc.subject 114 Physical sciences
dc.title Analysis of the magnetically induced current density of molecules consisting of annelated aromatic and antiaromatic hydrocarbon rings en
dc.type Article
dc.contributor.organization Department of Chemistry
dc.description.reviewstatus Peer reviewed
dc.relation.doi https://doi.org/10.1039/c6cp01968d
dc.relation.issn 1463-9076
dc.rights.accesslevel openAccess
dc.type.version publishedVersion

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