A Pd(II)-hydroxyporphycene: Synthesis, characterization, and photoinduced proton-coupled electron transfer

Toru Okawara, Masaaki Abe, Hisashi Shimakoshi, Yoshio Hisaeda

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)

Abstract

A Pd(II) complex, Pd(TPrPc-OH) (1, TPrPc-OH = 9-hydroxy-2,7,12,17- tetrapropylporphycenato dianion), has been synthesized and characterized. 1H NMR spectroscopy revealed that compound 1 exists as its enol form in solution. The H atom of the hydroxy group in 1 was exchanged with deuterium on addition of ethanol-d 6. UV-visible spectra showed a red shift of the Q band of 1 in THF compared with that of the acetoxy derivative Pd(TPrPc-OAc) (2, TPrPc-OAc = 9-acetoxy-2,7,12,17-tetrapropylporphycenato dianion). The pK a value of the hydroxy group in 1 was determined, by means of a UV-visible titration experiment, to be 10.56. A cyclic voltammogram of 1 in a mixture of THF and Britton-Robinson buffered aqueous solution revealed one-electron and one-proton coupled transfer in the oxidation process in the pH range from 2.7 to 10.5, which was identified by pH-varying experiments and the Pourbaix diagram. Transient absorption spectroscopy revealed that an electron-transfer reaction occurred from the triplet excited-state of 1 to 2,3,5,6-tetramethyl-1,4-benzoquinone (duroquinone, DQ) upon pulse laser irradiation at 532 nm. Such an intermolecular photoinduced electron-transfer reaction was not observed between the Ni analog, Ni(TPrPc-OH), and DQ. The reaction rate constant, k q, was indicative of a kinetic isotope effect with k q(H)/k q(D) = 1.7, supporting the belief that the exited-state electron transfer from 1 to DQ is accompanied by proton transfer.

Original languageEnglish
Pages (from-to)161-176
Number of pages16
JournalResearch on Chemical Intermediates
Volume39
Issue number1
DOIs
Publication statusPublished - Jan 2013

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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