Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)3(L)Br], where L = 1,10-phenanthroline (Phen–Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph–Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph–Re. It was found that the triplet metal-to-ligand charge-transfer dπ (Re) → π*(N-N) emission of Phen–Re and Pyph–Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen–Re and Pyph–Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom. According to the experimental and theoretical analysis, the red-shift of the photoluminescent spectrum and the lower LQY of Pyph–Re should be mainly attributed to the narrower energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital and the more LLCT transition ration of Pyph–Re, respectively.