The salts [Ru(bpy)(3)](PF6)(2), cis-[Ru(bpy)(2)(py)(2)](PF6)(2), trans-[Ru(bpy)(2)(4-Etpy)(2)](PF6)(2), [Ru(tpy)(2)](PF6)(2), and [Re(bpy)(CO)(3)(4-Etpy)](PF6) (bpy = 2,2'-bipyridine, py = pyridine, 4-Etpy = 4-ethylpyridine, and tpy = 2,2':6',2-terpyridine) have been incorporated into poly(methyl methacrylate) (PMMA) films and their photophysical properties examined by both steady-state and time-resolved absorption and emission measurements. Excited-state lifetimes for the metal salts incorporated in PMMA are longer and emission energies enhanced due to a rigid medium effect when compared to fluid CH3CN solution. In PMMA part of the fluid medium reorganization energy, lambda(oo), contributes to the energy gap with lambda(oo) similar to 700 cm(-1) for [Ru(bpy)(3)](PF6)(2) from emission measurements. Enhanced lifetimes can be explained by the energy gap law and the influence of the excited-to-ground state energy gap, E-o, on nonradiative decay. From the results of emission spectral fitting on [Ru(bpy)(3)](PF6)(2)* in PMMA, E-o is temperature dependent above 200 K with partial derivative E-o/partial derivative T = 2.8 cm(-1)/deg. cis-[Ru(bpy)(2)(py)(2)](PF6)(2) and trans-[Ru(bpy)(2)(4-Etpy)(2)](PF6)(2) are nonemissive in CH3CN and undergo photochemical ligand loss. Both emit in PMMA and are stable toward ligand loss even for extended photolysis periods. The lifetime of cis-[Ru(bpy)(2)(py)(2)](PF6)(2)* in PMMA is temperature dependent, consistent with a contribution to excited-state decay from thermal population and decay through a low-lying dd state or states. At temperatures above 190 K, coinciding with the onset of the temperature dependence of E-o for [Ru(bpy)(3)](PF6)(2)*, lifetimes become significantly nonexponential. The nonexponential behavior is attributed to dynamic coupling between MLCT and dd states, with the lifetime of the latter greatly enhanced in PMMA with tau similar to 3 ns. On the basis of these data and data in 4:1 (v/v) EtOH/MeOH, the energy gap between the MLCT and dd states is decreased by similar to 700 cm(-1) in PMMA with the dd state at higher energy by Delta H-0 similar to 1000 cm(-1). The "rigid medium stabilization effect" for cis-[Ru(bpy)(2)(py)(2)](PF6)(2)* in PMMA is attributed to inhibition of metal-ligand bond breaking and a photochemical cage effect.