Photoinduced Processes in Rhenium(I) Terpyridine Complexes Bearing Remote Amine Groups: New Insights from Transient Absorption Spectroscopy.

Photophysical properties of two Re(I) complexes [ReCl(CO)3(R-C6H4-terpy-κ2N)] with remote amine groups, N-methyl-piperazinyl (1) and (2-cyanoethyl)methylamine (2), were investigated. The complexes show strong absorption in the visible region corresponding to metal-to-ligand charge transfer (1MLCT) and intraligand-charge-transfer (1ILCT) transitions. The energy levels of 3MLCT and 3ILCT excited-states, and thus photoluminescence properties of 1 and 2, were found to be strongly affected by the solvent polarity. Compared to the parent chromophore [ReCl(CO)3(C6H5-terpy-κ2N)] (3), both designed complexes show significantly prolonged (by 1-2 orders of magnitude) phosphorescence lifetimes in acetonitrile and dimethylformamide, contrary to their lifetimes in less polar chloroform and tetrahydrofuran, which are comparable to those for 3. The femtosecond transient absorption (fsTA) measurements confirmed the interconversion between the 3MLCT and 3ILCT excited-states in polar solvents. In contrast, the emissive state of 1 and 2 in less polar environments is of predominant 3MLCT nature.