Reorganization energy of supramolecular donor-acceptor dyad of octaethylporphyrin isomers and axial-coordinated acceptor: Experimental and computational study

Mamoru Fujitsuka, Hisashi Shimakoshi, Yoshio Hisaeda, Tetsuro Majima

研究成果: Contribution to journalArticle査読

7 被引用数 (Scopus)

抄録

The internal reorganization energy (λV) of photoinduced electron transfer (ET) in the supramolecular donor-acceptor dyads of 2,3,7,8,12,13,17,18-octaethylporphinatozinc(II) (ZnOEP) and electron acceptor ligands was compared with those of structural isomers, 2,3,7,8,11,12,17,18- octaethylhemiporphycenatozinc(II) (ZnHPc) and 2,3,6,7,12,13,16,17- octaethylporphycenatozinc(II) (ZnPcn). First, ET process of the supramolecular donor-acceptor dyads of ZnOEP was investigated by means of the transient absorption spectroscopy mainly. The formation of supramolecular dyads was confirmed by absorption spectral change, from which the association constant was estimated. The ET process was confirmed by the observation of radical cation of ZnOEP during the laser flash photolysis. The ET rates of these dyads are in the order of ZnOEP > ZnHPc > ZnPcn, when the driving forces for ET are similar to each other. From the free energy dependence of ET rates, the λV values of OEP and its isomers were estimated. The estimated λV value was in the order of ZnOEP < ZnHPc < ZnPcn. This tendency was reproduced by calculation at B3LYP/6-31G(d) and BHandHLYP/6-31G(d) levels. The origin of this tendency was discussed on the basis of the structural change during the ET process.

本文言語英語
ページ(範囲)242-248
ページ数7
ジャーナルJournal of Photochemistry and Photobiology A: Chemistry
217
1
DOI
出版ステータス出版済み - 1 1 2011

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Physics and Astronomy(all)

フィンガープリント 「Reorganization energy of supramolecular donor-acceptor dyad of octaethylporphyrin isomers and axial-coordinated acceptor: Experimental and computational study」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル