Mechanical Modulation of the Solid‐State Luminescence of Tricarbonyl Rhenium(I) Complexes through the Interplay between Two Triplet Excited States

Abstract Mechanoresponsive luminescence (MRL) materials promise smart devices for sensing, optoelectronics and security. We present here the first report on the MRL activity of two Re I complexes, opening up new opportunities for applications in these fields. Both complexes exhibit marked solid‐state luminescence enhancement (SLE). Furthermore, the pristine microcrystalline powders emit in the yellow‐green region, and grinding led to an amorphous phase with concomitant emission redshift and shrinking of the photoluminescence (PL) quantum yields and lifetimes. Quantum chemical calculations revealed the existence of two low‐lying triplet excited states with very similar energy levels, that is, 3 IL and 3 MLCT, having, respectively, almost pure intraligand (IL) and metal‐to‐ligand charge‐transfer (MLCT) character. Transition between these states could be promoted by rotation around the pyridyltriazole−phenylbenzoxazole bond. In the microcrystals, in which rotations are hindered, the 3 IL state induces the prominent PL emission at short wavelengths. Upon grinding, rotation is facilitated and the transition to the 3 MLCT state results in a larger proportion of long‐wavelength PL. FTIR and variable‐temperature PL spectroscopy showed that the opening of the vibrational modes favours non‐radiative deactivation of the triplet states in the amorphous phase. In solution, PL only arises from the 3 MLCT state. The same mechanism accounts for the spectroscopic differences observed when passing from crystals to amorphous powders, and then to solutions, thereby clarifying the link between SLE and MRL for these complexes.