Photoluminescence Electron-Transfer Quenching of Rhenium(I) Rectangles with Amines
Resource
The Journal of Physical Chemistry A 110 (37): 10683-10689
Journal
The Journal of Physical Chemistry A
Journal Volume
110
Journal Issue
37
Pages
10683-10689
Date Issued
2006
Date
2006
Author(s)
Thanasekaran, P.
Liao, Rong-Tang
Manimaran, Bala.
Liu, Yen-Hsiang
Rajagopal, S.
Lu, Kuang-Lieh
Abstract
Electron-transfer (ET) reactions from aromatic amines to excited states of rhenium(I)-based molecular rectangles [{Re(CO)3(mu-bpy)Br}{Re(CO)3(mu-L)Br}]2 (bpy = 4,4'-bipyridine, L = 4,4'-dipyridylacetylene (dpa), I; L = 4,4'-dipyridylbutadiyne (dpb), II; and L = 1,4-bis(4'-pyridylethynyl)benzene (bpeb), III) were investigated in a dichloromethane solution using luminescence quenching techniques. Direct evidence for the ET reaction was obtained from the detection of the amine cation radical in this system using time-resolved transient absorption spectroscopy. The values of the luminescence quenching rate constants, kq, of the 3MLCT excited state of Re(I) rectangles with amines were found to be higher than those for the monomeric Re(I) complexes and other Re(I)-based metallacyclophanes. The observed kq values were correlated well with the driving force (Delta G degrees) for the ET reactions. In addition, a semiclassical theory of ET was successfully applied to the photoluminescence quenching of Re(I) rectangles with amines.
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Type
journal article
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