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Inorganic Chemistry, Vol.49, No.13, 5777-5779, 2010
1000-Fold Enhancement of Luminescence Lifetimes via Energy-Transfer Equilibration with the T-1 State of Zn(TPP)
The new zinc porphyrin/tungsten alkylidyne dyad Zn(TPP)-C equivalent to CC6H4C equivalent to W(dppe)(2)Cl (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) <- pi*(WCR)) phosphorescence with a lifetime that is 20 times longer than that of the parent chromophore W(CC6H4-CCPh)(dppe)(2)Cl (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.