Molecular structures, redox properties, and photosubstitution of ruthenium(II) carbonyl complexes of porphycene

Toru Okawara, Masaaki Abe, Shiho Ashigara, Yoshio Hisaeda

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Abstract

Two ruthenium(II) carbonyl complexes of porphycene, (carbonyl)(pyridine)(2,7,12,17-tetra-n-propylporphycenato)ruthenium(II) (1) and (carbonyl)(pyridine)(2,3,6,7,12,13,16,17-octaethylpor-phycenato)ruthenium(II) (2), have been structurally characterized by single-crystal X-ray diffraction analysis. Cyclic voltammetry has revealed that the porphycene complexes undergo multiple oxidations and reductions in dichloromethane and the reduction potentials are highly positive compared to porphyrin analogs. UV-light irradiation (400 nm or shorter wavelength region) of a benzene solution of 1 and 2 containing external pyridine leads to dissociation of the carbonyl ligand from the ruthenium(II) centers to give the corresponding bis-pyridine complexes. The identical reaction has been also studied for a porphyrin derivative (carbonyl)(pyridine)(2,3,7,8,12,13,17,18-octaethylporphyriato)ruthenum(II) (3). The first-order kinetic analysis has revealed that the photosubstitution of all of the compounds occurs in the order of 10-3 s-1 at 298 K but proceeds faster for complexes of porphycene (1 and 2) than that of porphyrin (3).

Original languageEnglish
Pages (from-to)233-241
Number of pages9
JournalJournal of Porphyrins and Phthalocyanines
Volume19
Issue number1-3
DOIs
Publication statusPublished - Jan 1 2015

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Ruthenium
Molecular structure
Porphyrins
Methylene Chloride
Benzene
Ultraviolet radiation
X ray diffraction analysis
Cyclic voltammetry
Oxidation-Reduction
pyridine
porphycene
Irradiation
Single crystals
Ligands
Derivatives
Wavelength
Oxidation
Kinetics

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Molecular structures, redox properties, and photosubstitution of ruthenium(II) carbonyl complexes of porphycene. / Okawara, Toru; Abe, Masaaki; Ashigara, Shiho; Hisaeda, Yoshio.

In: Journal of Porphyrins and Phthalocyanines, Vol. 19, No. 1-3, 01.01.2015, p. 233-241.

Research output: Contribution to journalArticle

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