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Abstract
Highly resolved emission, excitation, and absorption spectra of [Os(bpy)3]2+ doped into a single-crystal [Ru(bpy)3]X2 matrix with X = PF6, AsF6, SbF6 are presented for low temperatures (2 ˇ- T ˇ- 16 K). This comprehensive information allows a reliable spectroscopic identification of different sites and several electronic zero-phonon transitions. Three distinct sites of [Os(bpy)3]2+ are identified for every compound. For X - = PF- 6 and AsF- 6 site-selective emission spectra of the sites of lowest energy (called A) could be registered. Further, different excited (and emitting) electronic states are identified for every site. The second excited state |II> lies between 61 and 76 cm-1 above the lowest one |I>, depending on the specific site and the counterion. The energies of both excited states are determined from their zero-phonon lines. A further very weak transition, which possibly is connected to an additional electronic state |Γ>, is detected 5 to 9 cm-1 (depending on X - and the site) above |I>. From the emission spectra of high resolution it is found that the transition |I> → |0> of [Os(bpy)3]2+ couples to a very large number of vibrational satellites. Most of these vibrations are also found in the I.R. spectrum of [Os(bpy)3](PF6)2.