Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Shunichi Fukuzumi | * |
dc.date.accessioned | 2016-08-28T12:08:22Z | - |
dc.date.available | 2016-08-28T12:08:22Z | - |
dc.date.issued | 2011 | * |
dc.identifier.issn | 0947-6539 | * |
dc.identifier.other | OAK-7398 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/221469 | - |
dc.description.abstract | A 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.language | English | * |
dc.title | Greatly enhanced intermolecular π-dimer formation of a porphyrin trimer radical trications through multiple πbonds | * |
dc.type | Article | * |
dc.relation.issue | 12 | * |
dc.relation.volume | 17 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 3420 | * |
dc.relation.lastpage | 3428 | * |
dc.relation.journaltitle | Chemistry - A European Journal | * |
dc.identifier.doi | 10.1002/chem.201002822 | * |
dc.identifier.wosid | WOS:000288099200018 | * |
dc.identifier.scopusid | 2-s2.0-79952426325 | * |
dc.author.google | Takai A. | * |
dc.author.google | Gros C.P. | * |
dc.author.google | Barbe J.-M. | * |
dc.author.google | Fukuzumi S. | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.date.modifydate | 20240401081001 | * |