Contrasts between the Vibronic Contributions in the tris-(2,2′-bipyridyl)Osmium(II) Emission Spectrum and the Implications of Resonance-Raman Parameters

Abstract

The emission spectrum of the tris-(2,2'-bipyridine)osmium(II) metal-to-ligand charge transfer (MLCT) excited-state frozen solution at 77 K differs qualitatively from that expected based on its reported resonance-Raman (rR) parameters in that (1) the dominant vibronic contributions to the emission spectrum are in the low frequency regime (corresponding to nuclear displacements in largely to metal-ligand vibrational modes) and these contributions are negligible in the rR; and (2) the amplitude of the emission sideband components that correspond to envelopes of largely bpy centered vibrational modes is about 40% of that expected (relative to the amplitude observed for the band origin) for a simple vibronic progression in these modes. The distortions in low frequency vibrational modes are attributable to configurational mixing between metal centered (LF) and MLCT excited states, and the small amplitudes of the bpy-mode vibronic components may be a consequence of some intrinsic differences of the distortions of the (3)MLCT and (1)MLCT excited states such as the zero-field splitting of the (3)MLCT excited state and the different distortions of these excited-state components.