Excited-State Relaxation in Luminescent Molybdenum(0) Complexes with Isocyanide Chelate Ligands

Diisocyanide ligands with a m-terphenyl backbone provide access to Mo0 complexes exhibiting the same type of metal-to-ligand charge transfer (MLCT) luminescence as the well-known class of isoelectronic RuII polypyridines. The luminescence quantum yields and lifetimes of the homoleptic tris(diisocyanide) Mo0 complexes depend strongly on whether methyl- or tert-butyl substituents are placed in α-position to the isocyanide groups. The bulkier tert-butyl substituents lead to a molecular structure in which the three individual diisocyanides ligated to one Mo0 center are interlocked more strongly into one another than the ligands with the sterically less demanding methyl substituents. This rigidification limits the distortion of the complex in the emissive excited-state, causing a decrease of the nonradiative relaxation rate by one order of magnitude. Compared to RuII polypyridines, the molecular distortions in the luminescent 3MLCT state relative to the electronic ground state seem to be smaller in the Mo0 complexes, presumably due to delocalization of the MLCT-excited electron over greater portions of the ligands. Temperature-dependent studies indicate that thermally activated nonradiative relaxation via metal-centered excited states is more significant in these homoleptic Mo0 tris(diisocyanide) complexes than in [Ru(2,2′-bipyridine)3]2+