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Title: Electronic energy transfer from the charge-transfer excited states of ruthenium(II) polypyridyl complexes to the ligand field excited states of chromium(III). Weakly coupled small energy gap behavior for bimolecular reactions

Abstract

Interpretation of the rate patterns previously reported for the energy-transfer quenching of (*CT)Ru(bpy)/sub 3//sup 2 +/ and (*CT)-Ru(bpy)/sub 2/(CN)/sub 2/ (bpy = 2,2'-bipyridyl) donors by chromium(III) complexes is generally complicated by appreciable overlap of the donor (*CT ..-->.. /sup 1/A/sub 1/) emission and the acceptor (/sup 4/T/sub 2/ reverse arrow /sup 4/A/sub 2/) absorbance. To avoid the resulting ambiguities of interpretation, rate patterns have been determined for a series of Cr(III) amine and cyanoamine complexes for which the spectral overlap is very small and only doublet acceptor states are energetically accessible. The resulting quenching rates are much smaller than the expected diffusion limit, and they tend to increase in proportion to the donor-acceptor energy gap, ..delta.. E. This is an expected result for ..delta.. E less than the energies of available acceptor vibrational modes due to the increase of the density of acceptor states with increasing ..delta.. E. When there is appreciable donor-acceptor spectral overlap, a quartet quenching channel appears to compete, with the net quenching rate a composite of the doublet and quartet channels. 39 references, 5 figures, 1 table.

Authors:
;
Publication Date:
Research Org.:
Wayne State Univ., Detroit, MI
OSTI Identifier:
6037411
Resource Type:
Journal Article
Journal Name:
J. Phys. Chem.; (United States)
Additional Journal Information:
Journal Volume: 90:6
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHROMIUM COMPLEXES; EXCITED STATES; RADIATIONLESS DECAY; PYRIDINES; RUTHENIUM COMPLEXES; ABSORPTION; ADDUCTS; ELECTRON TRANSFER; EMISSION; ENERGY TRANSFER; EXPERIMENTAL DATA; LIGANDS; AZINES; COMPLEXES; DATA; DE-EXCITATION; ENERGY LEVELS; ENERGY-LEVEL TRANSITIONS; HETEROCYCLIC COMPOUNDS; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; TRANSITION ELEMENT COMPLEXES; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)

Citation Formats

Tamilarasan, R., and Endicott, J.F. Electronic energy transfer from the charge-transfer excited states of ruthenium(II) polypyridyl complexes to the ligand field excited states of chromium(III). Weakly coupled small energy gap behavior for bimolecular reactions. United States: N. p., 1986. Web. doi:10.1021/j100278a013.
Tamilarasan, R., & Endicott, J.F. Electronic energy transfer from the charge-transfer excited states of ruthenium(II) polypyridyl complexes to the ligand field excited states of chromium(III). Weakly coupled small energy gap behavior for bimolecular reactions. United States. doi:10.1021/j100278a013.
Tamilarasan, R., and Endicott, J.F. Thu . "Electronic energy transfer from the charge-transfer excited states of ruthenium(II) polypyridyl complexes to the ligand field excited states of chromium(III). Weakly coupled small energy gap behavior for bimolecular reactions". United States. doi:10.1021/j100278a013.
@article{osti_6037411,
title = {Electronic energy transfer from the charge-transfer excited states of ruthenium(II) polypyridyl complexes to the ligand field excited states of chromium(III). Weakly coupled small energy gap behavior for bimolecular reactions},
author = {Tamilarasan, R. and Endicott, J.F.},
abstractNote = {Interpretation of the rate patterns previously reported for the energy-transfer quenching of (*CT)Ru(bpy)/sub 3//sup 2 +/ and (*CT)-Ru(bpy)/sub 2/(CN)/sub 2/ (bpy = 2,2'-bipyridyl) donors by chromium(III) complexes is generally complicated by appreciable overlap of the donor (*CT ..-->.. /sup 1/A/sub 1/) emission and the acceptor (/sup 4/T/sub 2/ reverse arrow /sup 4/A/sub 2/) absorbance. To avoid the resulting ambiguities of interpretation, rate patterns have been determined for a series of Cr(III) amine and cyanoamine complexes for which the spectral overlap is very small and only doublet acceptor states are energetically accessible. The resulting quenching rates are much smaller than the expected diffusion limit, and they tend to increase in proportion to the donor-acceptor energy gap, ..delta.. E. This is an expected result for ..delta.. E less than the energies of available acceptor vibrational modes due to the increase of the density of acceptor states with increasing ..delta.. E. When there is appreciable donor-acceptor spectral overlap, a quartet quenching channel appears to compete, with the net quenching rate a composite of the doublet and quartet channels. 39 references, 5 figures, 1 table.},
doi = {10.1021/j100278a013},
journal = {J. Phys. Chem.; (United States)},
number = ,
volume = 90:6,
place = {United States},
year = {1986},
month = {3}
}