Low Temperature Emissive Cyclometalated Cobalt(III) Complexes.

A series of Co complexes [Co(ImP)][PF], with HImP = 1,1'-(1,3-phenylene)bis(3-methyl-1-imidazole-2-ylidene)) and R = Me, Et, Pr, Bu, is presented in this work. The influence of the strong donor ligand on the ground and excited-state photophysical properties was investigated in the context of different alkyl substituents at the imidazole nitrogen. X-ray diffraction revealed no significant alterations of the structures and all differences in the series emerge from the electronic structures. These were probed via cyclic voltammetry and UV-vis spectroscopy, detailing the influence of the different alkyl substituents on the ground-state properties. All complexes are emissive at 77 K from a MC state, which exhibits lifetimes in the range of 1-5 ns at room temperature, depending on the alkyl substituent. Therefore, it is clearly shown that even small differences in the electronic structure have a large impact on the details of the excited state landscape. The observed behavior was rationalized by a detailed DFT analysis, which shows that the minimum-energy crossing point to the ground-state is located only slightly above the MC energy: Consequently, nonradiative decay to the ground state at room temperature is enabled, while at 77 K this path is prohibited, leading to low-temperature MC emission.