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An apparent angle dependence for the nonradiative deactivation of excited triplet states of sterically constrained, binuclear ruthenium(II) bis(2,2′:6′,2″-terpyridine) complexes

Lookup NU author(s): Professor Andrew Benniston, Emeritus Professor Anthony Harriman, Dr Peiyi Li, Pritesh Patel, James Rostron, Craig Sams


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The photophysical properties are reported for a series of binuclear ruthenium(II) bis(2,2′:6′,2″-terpyridine) complexes built around a geometrically constrained, biphenyl-based bridge. The luminescence quantum yield and lifetime increase progressively with decreasing temperature, but the derived rate constant for nonradiative decay of the lowest-energy triplet state depends on the length of a tethering strap attached at the 2,2′-positions of the biphenyl unit. Since the length of the strap determines the dihedral angle for the central C-C bond, the rate of nonradiative decay shows a pronounced dependence on angle. The minimum rate of nonradiative decay occurs when the dihedral angle is 90°, but there is a maximum in the rate when the dihedral angle is about 45°. This effect does not appear to be related to the extent of electron delocalization at the triplet level but can be explained in terms of variable coupling with a low-frequency vibrational mode associated with the strapped biphenyl unit. © 2006 American Chemical Society.

Publication metadata

Author(s): Benniston AC, Harriman A, Li P, Patel PV, Rostron JP, Sams CA

Publication type: Article

Publication status: Published

Journal: Journal of Physical Chemistry A

Year: 2006

Volume: 110

Issue: 32

Pages: 9880-9886

ISSN (print): 1089-5639

ISSN (electronic): 1520-5215

Publisher: American Chemical Society


DOI: 10.1021/jp061059g


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