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The excited-state dynamics of seven new platinum(II) complexes have been investigated by a range of spectroscopic techniques. The complexes include (a) two platinum(II) diimine complexes with electron-donating (phenylethynyl and 1-methyl-1H-imidazole) or electron-withdrawing (2,5-dicyanophenyl) substituents, (b) one platinum(II) diimine complex with a bulky, electron-rich moiety, (c) a platinum(II) complex of a 1,4-disubstituted naphthalene dye, and (d) a platinum(II) complex of a rhodamine dye. For all complexes, the strong absorption band in the near-infrared region has a mixed metal-ligand character, with a metal-to-ligand charge transfer contribution and a singlet-singlet metal-to-ligand charge transfer contribution, and a minor contribution from a (3)MC intermediate. Two of the complexes (the complexes with 1-methyl-1H-imidazole and 2,5-dicyanophenyl substituents) have a weak absorption band in the visible region. For each of these complexes, a spectral feature is observed between 1200 and 1300 nm that has a negative temperature coefficient of the observed intensity. Comparison of the rate constant of the first triplet-state decay (k(T)(1)) with the rate constant of the reverse electron transfer process (k(ET)) shows that efficient ET

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