1000-Fold Enhancement of Luminescence Lifetimes via Energy-Transfer Equilibration with the T1 State of Zn(TPP)

The new zinc porphyrin/tungsten alkylidyne dyad Zn(TPP)−CCC6H4CW(dppe)2Cl (1) possesses novel photophysical properties that arise from a tunable excited-state triplet−triplet equilibrium between the porphyrin and tungsten alkylidyne units. Dyad 1 exhibits 3(d xy ← π*(WCR)) phosphorescence with a l...

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Bibliographic Details
Published in:Inorganic chemistry 2010-07, Vol.49 (13), p.5777-5779
Main Authors: Cohen, Brian W, Lovaasen, Benjamin M, Simpson, Cheslan K, Cummings, Scott D, Dallinger, Richard F, Hopkins, Michael D
Format: Article
Language:English
Online Access:Get full text
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Summary:The new zinc porphyrin/tungsten alkylidyne dyad Zn(TPP)−CCC6H4CW(dppe)2Cl (1) possesses novel photophysical properties that arise from a tunable excited-state triplet−triplet equilibrium between the porphyrin and tungsten alkylidyne units. Dyad 1 exhibits 3(d xy ← π*(WCR)) phosphorescence with a lifetime that is 20 times longer than that of the parent chromophore W(CC6H4CCPh)(dppe)2Cl (2). The triplet−triplet equilibrium can be tuned by the addition of ligands to the Zn center, resulting in phosphorescence lifetimes for 1(L) that are up to 1300 times longer than that of 2. The “lifetime reservoir” effect exhibited by 1(L) is approximately 1 order of magnitude larger than previously reported examples of the phenomenon.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic100316s