fac-Re(CO)3Cl Complexes of [2-(4-R‑1H‑1,2,3-Triazol-1-yl)methyl]pyridine Inverse “Click” Ligands: A Systematic Synthetic, Spectroscopic, and Computational Study

A series of electronically tuned fac-Re­(CO)3Cl inverse pyridyl-1,2,3-triazole complexes have been synthesized in good to excellent yields (72–95%) by refluxing methanol solutions of [Re­(CO)5Cl] and the substituted [2-(4-R-1H-1,2,3-triazol-1-yl)­methyl]­pyridine ligands (py­(CH2)­tri-R). The resulting rhenium­(I) complexes were characterized by elemental analysis, HR-ESI-MS and IR and 1H and 13C NMR spectroscopy. Additionally, the molecular structures of three of the complexes were confirmed using X-ray crystallography. The electronic properties of this series of fac-[(py­(CH2)­tri-R)­Re­(CO)3Cl] complexes were examined using UV–vis, Raman, and emission spectroscopy and cyclic voltammetry techniques. The complexes exhibit intense absorptions in the UV region, which were modeled using time-dependent density functional theory (TD-DFT). The calculations suggest that the lower energy part of the absorption band is MLCT in nature and additional higher energy π–π* transitions are present. The electronic spectra are nearly identical for all except where R = 4-nitrophenyl, suggesting that the 1,2,3-triazolyl unit acts as an electronic insulator. The TD-DFT calculations suggest that the lowest energy MLCT transition is polarized to the pyridine moiety for all complexes except the nitro-substituted one. With R = 4-nitrophenyl the MLCT is directed to an acceptor MO polarized to the triazole-R moiety. This finding is supported by resonance Raman studies that show enhancement of modes associated with the triazole-R group. The complexes are weakly emissive at room temperature with quantum yields –3 and correspondingly short excited-state lifetimes (τ H-1,2,3-triazol-1-yl)­pyridine substituent.