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Influence of Triplet Surface Properties on Excited-State Deactivation of Expanded Cage Bis(tridentate)Ruthenium(II) Complexes.

Calculations of excited-state potential energy surfaces (PESs) are useful to predict key properties relating to the deactivation cascade of transition-metal complexes. Here, we first perform full free optimizations of the relevant excited-state minima, followed by extensive two-dimensional PES calculations based on the minima of interest. Maps of the lowest triplet excited-state surfaces of two bistridentate RuII-complexes, [Ru(DQP)2]2+ and [Ru(DQzP)2]2+, are used to explain recent experimental findings including an unexpected order of magnitude difference in an excited-state lifetime. The calculations reveal significant differences in the fundamental shapes and spin transitions of the lowest triplet excited-state energy surfaces of the two complexes and, in particular, show that the metal-to-ligand charge transfer (MLCT) surface region of [Ru(DQzP)2]2+ with a shorter excited-state lifetime is significantly smaller than that of [Ru(DQP)2]2+. This leads to a minimum energy crossing between the triplet and singlet surfaces near the MLCT for [Ru(DQzP)2]2+ or near the MC for [Ru(DQP)2]2+. These results indicate that the experimentally observed difference in the excited-state lifetime is closely related to the set of energetically accessible 3MLCT conformations.