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Excited state redox properties of phthalocyanines: influence of the axial ligand on the rates of relaxation and electron-transfer quenching of the lowest /sup 3/. pi pi. /sup */ excited state

Journal Article:

Abstract

Laser flash excitations at 640 nm have been used to generate the transient spectra of the lowest-lying /sup 3/..pi pi../sup */ state of phthalocyaninatoruthenium(II) complexes. The properties of this excited state such as the properties of the maxima, lambda/sub max/ = 500 +/- 30 nm, and lifetimes, t/sub 1/2/ = 70-4500 ns, exhibit a large dependence on the electron-accepting and electron-withdrawing tendencies of the axial ligands. A similar influence was observed upon the rate of electron-transfer quenching of the /sup 3/..pi pi../sup */ state. Values between 10/sup 6/ and 10/sup 7/ dm/sup 3/ mol/sup -1/ s/sup -1/ for the self-exchange rate constant have been obtained, according to Marcus-Hush theoretical treatments, for (Ru(pc.)LL')/sup +//(/sup 3/..pi pi../sup */)(Ru(pc)LL') (L and L' = neutral axial ligands; pc = phthalocyaninate (2-)) and isoelectronic cobalt(III) and rhodium(III) couples. The redox properties of the ground and excited states are correlated with axial ligand-induced perturbations of the electronic structure.
Publication Date:
Jan 01, 1874
Product Type:
Journal Article
Reference Number:
EDB-87-016366
Resource Relation:
Journal Name: J. Chem. Soc., Dalton Trans.; (United Kingdom)
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; PHTHALOCYANINES; ELECTRONIC STRUCTURE; EXCITED STATES; REDOX REACTIONS; CHEMICAL REACTION KINETICS; ELECTRON TRANSFER; EXPERIMENTAL DATA; LASERS; LIGANDS; RADIATIONLESS DECAY; CHEMICAL REACTIONS; DATA; DE-EXCITATION; DYES; ENERGY LEVELS; ENERGY TRANSFER; ENERGY-LEVEL TRANSITIONS; HETEROCYCLIC COMPOUNDS; INFORMATION; KINETICS; NUMERICAL DATA; ORGANIC COMPOUNDS; REACTION KINETICS; 400500* - Photochemistry; 400201 - Chemical & Physicochemical Properties
OSTI ID:
7223952
Research Organizations:
Univ. of Notre Dame, IN
Country of Origin:
United Kingdom
Language:
English
Other Identifying Numbers:
Journal ID: CODEN: JCDTB
Submitting Site:
JMT
Size:
Pages: 2137-2140
Announcement Date:

Journal Article:

Citation Formats

Ferraudi, G J, and Prasad, D R. Excited state redox properties of phthalocyanines: influence of the axial ligand on the rates of relaxation and electron-transfer quenching of the lowest /sup 3/. pi pi. /sup */ excited state. United Kingdom: N. p., 1874. Web.
Ferraudi, G J, & Prasad, D R. Excited state redox properties of phthalocyanines: influence of the axial ligand on the rates of relaxation and electron-transfer quenching of the lowest /sup 3/. pi pi. /sup */ excited state. United Kingdom.
Ferraudi, G J, and Prasad, D R. 1874. "Excited state redox properties of phthalocyanines: influence of the axial ligand on the rates of relaxation and electron-transfer quenching of the lowest /sup 3/. pi pi. /sup */ excited state." United Kingdom.
@misc{etde_7223952,
title = {Excited state redox properties of phthalocyanines: influence of the axial ligand on the rates of relaxation and electron-transfer quenching of the lowest /sup 3/. pi pi. /sup */ excited state}
author = {Ferraudi, G J, and Prasad, D R}
abstractNote = {Laser flash excitations at 640 nm have been used to generate the transient spectra of the lowest-lying /sup 3/..pi pi../sup */ state of phthalocyaninatoruthenium(II) complexes. The properties of this excited state such as the properties of the maxima, lambda/sub max/ = 500 +/- 30 nm, and lifetimes, t/sub 1/2/ = 70-4500 ns, exhibit a large dependence on the electron-accepting and electron-withdrawing tendencies of the axial ligands. A similar influence was observed upon the rate of electron-transfer quenching of the /sup 3/..pi pi../sup */ state. Values between 10/sup 6/ and 10/sup 7/ dm/sup 3/ mol/sup -1/ s/sup -1/ for the self-exchange rate constant have been obtained, according to Marcus-Hush theoretical treatments, for (Ru(pc.)LL')/sup +//(/sup 3/..pi pi../sup */)(Ru(pc)LL') (L and L' = neutral axial ligands; pc = phthalocyaninate (2-)) and isoelectronic cobalt(III) and rhodium(III) couples. The redox properties of the ground and excited states are correlated with axial ligand-induced perturbations of the electronic structure.}
journal = {J. Chem. Soc., Dalton Trans.; (United Kingdom)}
journal type = {AC}
place = {United Kingdom}
year = {1874}
month = {Jan}
}