Diagnosis of Magnetoresponsive Aromatic and Antiaromatic Zones in Three-Membered Rings of d- and f-Block Elements

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dc.contributor.authorTsipis, A. C.en
dc.contributor.authorDepastas, I. G.en
dc.contributor.authorKaragiannis, E. E.en
dc.contributor.authorTsipis, C. A.en
dc.date.accessioned2015-11-24T16:56:07Z
dc.date.available2015-11-24T16:56:07Z
dc.identifier.issn0192-8651-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/10393
dc.rightsDefault Licence-
dc.subjectaromaticityen
dc.subjectdft calculationsen
dc.subjectnics(zz)-scan profilesen
dc.subjectaromatic zonesen
dc.subjectantiaromatic zonesen
dc.subjectaromaticity of d- and f-block clustersen
dc.subjectindependent chemical-shiftsen
dc.subjectzeta-valence qualityen
dc.subjectgaussian-basis setsen
dc.subjectcurrent-densityen
dc.subjectcontinuous transformationen
dc.subjectelectron delocalizationen
dc.subjectorbital contributionsen
dc.subjectmagnetic-propertiesen
dc.subjectnics profilesen
dc.subjectatoms lien
dc.titleDiagnosis of Magnetoresponsive Aromatic and Antiaromatic Zones in Three-Membered Rings of d- and f-Block Elementsen
heal.abstractMagnetoresponsive three-membered rings of d- and f-block elements have been thoroughly investigated with file help of electronic structure calculation methods. The magnetic response of the clusters was evaluated by the Nucleus Independent Chemical Shifts (NICS)(zz)-scan curves, which in conjunction with symmetry-based selection rules for the most significant translationally and rotationally allowed transitions helped rationalize and predict the orbital-type of aromaticity/antiaromaticity of the clusters. The magnetoresponsive early (Groups 3, 4, and 5) transition metal M(3) rings exhibit successive aromatic and antiaromatic zones separated by a nodal plane. The magnetoresponsive late (Groups 11 and 12) transition metal M(3) rings exhibit long-range aromatic zone with the NICS(zz)(R) values decaying rapidly and monotonically with respect to R. The magnetic response of Group 10 transition metal M(3) rings is similar to that of the early transition metal M(3) rings, but it is long-range antiaromatic only for the [c-Ni(3)] cluster. The NICS(zz)-scan curve of the [(H(t)La)(3)(mu(2)-H)(6)] cluster is indicative of weak pure sigma-aromaticity due to the induced diatropic ring current from the translationally allowed a(1)' -> e' and e' -> a(1)' transitions. The aromatic-antiaromatic behavior of the [(H(t)Ce)(3)(mu(2)-H)(6)](+) and [(H(t)Tm)(3)(mu(2)-H)(6)](2-) clusters is similar to that of the early d-block elements. The magnetic response of [(H(t)Yb)(3)(mu(2)-H)(6)](3-) is similar to that of [c-Hg(3)](2-). The [(H(t)Lu)(3)(mu(2)-H)(6)] cluster can be considered as a doubly (sigma + pi) aromatic system, with the sigma-aromatic component being much stronger than the pi-aromatic one. Finally, the [(X(t)Re)(3)(mu(2)-X)(6)] and [(X(t)Ru)(3)(mu(2)-X)(6)](+) (X = Cl, Br, I) clusters exhibit significant aromatic character with the greatest contribution to the induced diatropic ring currents coming from pi-type transitions. (C) 2009 Wiley Periodicals, Inc. J Comput Chem 31: 431-446, 2010en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDoi 10.1002/Jcc.21327-
heal.identifier.secondary<Go to ISI>://000273412900018-
heal.identifier.secondaryhttp://onlinelibrary.wiley.com/store/10.1002/jcc.21327/asset/21327_ftp.pdf?v=1&t=h0f911xv&s=7f82a949e6ebd560fe88a88bdf26e0d0428b1505-
heal.journalNameJournal of Computational Chemistryen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2010-
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείαςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

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