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

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http://hdl.handle.net/10138/224360

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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

Titel: Analysis of the magnetically induced current density of molecules consisting of annelated aromatic and antiaromatic hydrocarbon rings
Författare: Sundholm, Dage; Berger, Raphael J. F.; Fliegl, Heike
Upphovmannens organisation: Department of Chemistry
Datum: 2016-06-21
Språk: eng
Sidantal: 9
Tillhör serie: Physical Chemistry Chemical Physics
ISSN: 1463-9076
DOI: https://doi.org/10.1039/c6cp01968d
Permanenta länken (URI): http://hdl.handle.net/10138/224360
Abstrakt: 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.
Subject: INDEPENDENT CHEMICAL-SHIFTS
INCLUDING ATOMIC ORBITALS
CURRENT MODEL
WORKSTATION COMPUTERS
PERTURBATION-THEORY
GLOBAL-MINIMUM
PI-SYSTEMS
BASIS-SETS
ENERGY
NAPHTHALENE
116 Chemical sciences
114 Physical sciences
Referentgranskad: Ja
Licens: cc_by_nc
Användningsbegränsning: openAccess
Parallelpublicerad version: publishedVersion


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