Abstract
Surface adsorption of transition-metal polypyridyl complexes on highly luminescent, anodized porous silicon (p-Si) wafers leads to dramatic quenching of the emission. Facile energy transfer occurs from the surface to adsorbed complexes of RuII and OsII. Photoluminescence (PL) from underivatized p-Si is excitation- and monitoring-wavelength-dependent. A phenomenological model is proposed to explain these observations in which intercluster energy transfer occurs by an energy-transfer cascade, and there is weak kinetic coupling to even lower-energy surface emitters. Adsorption of [Zn(dmb)3](PF6)2 (dmb is 4,4‘-dimethyl-2,2‘-bipyridine) or fac-[Re(bpy)(CO)3(4-Etpy)](PF6)2 (bpy is 2,2‘-bipyridine; 4-Etpy is 4-ethylpyridine), possibly by ion-exchange, results in quenching of the low-energy surface emitters. For adsorbed [MII(bpy)2(4-CO2H-4‘Mebpy)](PF6)2 (M = Ru, Os; 4-CO2H-4‘Mebpy is 4-carboxylic acid-4‘-methyl-2,2‘-bipyridine), p-Si* → MII energy transfer occurs to low-lying metal-to-ligand charge-transfer (MLC...
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