View : 93 Download: 0

Full metadata record

DC Field Value Language
dc.contributor.authorShunichi Fukuzumi-
dc.date.accessioned2016-08-28T12:08:22Z-
dc.date.available2016-08-28T12:08:22Z-
dc.date.issued2011-
dc.identifier.issn0947-6539-
dc.identifier.otherOAK-7398-
dc.identifier.urihttp://dspace.ewha.ac.kr/handle/2015.oak/221469-
dc.description.abstractA trefoil-like porphyrin trimer linked by triphenylamine (TPA-TPZn 3) was synthesized. A three-electron oxidation of TPA-TPZn 3 forms a radical trication (TPA-TPZn 3 3+), in which each porphyrin ring undergoes a one-electron oxidation. The radical trication TPA-TPZn 3 3+ spontaneously dimerizes to afford (TPA-TPZn 3) 2 6+ in CH 2Cl 2. The characteristic charge-resonance band due to the charge delocalization over the πsystem of (TPA-TPZn 3) 2 6+ was observed in the NIR region. The initial oxidation potential of TPA-TPZn 3 is negatively shifted relative to that of the corresponding monomer porphyrin, which results from the stabilization of the oxidized state of TPA-TPZn 3 associated with the dimerization. The thermodynamic parameters (i.e., ΔH, ΔS, and ΔG) for the formation of (TPA-TPZn 3) 2 6+ were determined by measuring Vis/NIR spectra at various temperatures. The formation constant of (TPA-TPZn 3) 2 6+ is significantly larger than that of the radical cation dimer of the corresponding monomer porphyrin (e.g., over 2000-fold at 233K). The electronic states were investigated using EPR spectroscopic analysis. The greatly enhanced dimerization of TPA-TPZn 3 3+ results from multiple π-bond formation between the porphyrin radical cations. Multiple π bonds: A three-electron oxidation of a trefoil-like porphyrin trimer generates a radical trication, which spontaneously dimerizes. The dimerization of the trimer is much more favorable relative to the corresponding monomer, which results from the intermolecular multiple π-bond formation between porphyrin radical cations of the trimer (see picture). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.-
dc.languageEnglish-
dc.titleGreatly enhanced intermolecular π-dimer formation of a porphyrin trimer radical trications through multiple πbonds-
dc.typeArticle-
dc.relation.issue12-
dc.relation.volume17-
dc.relation.indexSCI-
dc.relation.indexSCIE-
dc.relation.indexSCOPUS-
dc.relation.startpage3420-
dc.relation.lastpage3428-
dc.relation.journaltitleChemistry - A European Journal-
dc.identifier.doi10.1002/chem.201002822-
dc.identifier.wosidWOS:000288099200018-
dc.identifier.scopusid2-s2.0-79952426325-
dc.author.googleTakai A.-
dc.author.googleGros C.P.-
dc.author.googleBarbe J.-M.-
dc.author.googleFukuzumi S.-
dc.contributor.scopusidShunichi Fukuzumi(35430038100)-
dc.date.modifydate20200403081004-
Appears in Collections:
자연과학대학 > 화학·나노과학전공 > Journal papers
Files in This Item:
There are no files associated with this item.
Export
RIS (EndNote)
XLS (Excel)
XML


qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE