9 February 1995 Intramolecular energy transfer and excitation coupling in metal-to-ligand charge transfer (MLCT) excited states
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Proceedings Volume 2362, International Conference on Excitonic Processes in Condensed Matter; (1995) https://doi.org/10.1117/12.200972
Event: Excitonic Processes in Condensed Matter: International Conference, 1994, Darwin, Australia
Several new spectroscopic studies relating to the coupling and dynamics in the spin-forbidden 3MLCT excited states of the chromophores [Ru(bpy)3]2+ and [Os(bpy)3]2+ (bpy equals 2,2'-bipyridine) in the racemic crystal lattices [Ru(bpy)3](PF6)2, [Ru(bpy)3](ClO4)2 and [Zn(bpy)3](ClO4)2 are presented. In the first of these lattices there are three closely related chromophoric sites at low temperatures, each with trigonal (C3) symmetry. In the two, isomorphic perchlorate salts there is a single chromophoric site, which has C2 symmetry. Using time resolved luminescence line narrowing, we have been able to directly measure the excitation transfer rate between two equivalent metal-ligand units in the [Ru(bpy)3]2+ chromophore doped in the [Zn(bpy)3](ClO4)2 lattice. The rate obtained (approximately equals 1 X 108 sec-1) is in excellent accord with estimates made from the observed linewidth in Stark swept transient hole-burning experiments made on the same system and confirm the single ligand, localized nature of the lowest emitting excited states and thus the very weak intramolecular coupling between metal ligand sub-units within this chromophore. The corresponding coupling in the [Os(bpy)3]2+ system is stronger and, in contrast to the ruthenium analogue, gives rise to additional features in the optical spectra in the origin region of the lowest 3MLCT excited states. The magnitude of the coupling can be probed and assessed by preparing modified chromophoric materials, in which one or two of the bpy ligands are perdeuterated (bpy-d8). This selective deuteration breaks the (near) degeneracy of excitations involving crystallographically equivalent ligands by approximately equals 30 - 40 cm-1 and this competes with or completely overrides the exciton coupling process. The exciton coupling is found to be approximately equals 2.4 cm-1 for [Os(bpy)3]2+ doped in [Ru(bpy)3](PF6)2 and can be understood within a mini-exciton description. Stronger couplings for the same chromophore in [Zn(bpy)3](ClO4)2 are indicated in our preliminary results. In inhomogeneously broadened systems such as frozen glasses or solutions, in which MLCT excitations involving different ligands on the same chromophore may differ in energy by 100 cm-1 or more, an effectively localized description of the low lying 3MLCT states is appropriate for [Os(bpy)3]2+.
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Hans Riesen, Hans Riesen, Elmars Krausz, Elmars Krausz, "Intramolecular energy transfer and excitation coupling in metal-to-ligand charge transfer (MLCT) excited states", Proc. SPIE 2362, International Conference on Excitonic Processes in Condensed Matter, (9 February 1995); doi: 10.1117/12.200972; https://doi.org/10.1117/12.200972

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