Anion-Recognition Studies of a Rhenium(I) 4-Mercaptopyridine Compound and Its Ligand-Coupling Products

The reaction of Re(CO)₅Cl with 4-mercaptopyridine (4-PySH) led to the formation of [Re(CO)₃(4-HPyS)₃]Cl (1), showing three hydrogen-bonding donors of 4-PySH ligands as well as a characteristic ligand-to-metal charge-transfer absorption at ca. 380 nm. In this regard, a variety of anions, i.e., CN^-, OAc^-, F^-, Cl^-, Br^-, I^-, PF₆^-, NO₃^-, ClO₄^-, and H₂PO₄^-, were examined to study anion-recognition studies through hydrogen-bonding functionalities. Upon the addition of CN^- to a methanolic solution of complex 1, a remarkable spectral change with an isosbestic point at ca. 314 nm in the absorption spectra was observed, with a binding constant (K_b) calculated to be 24770 M^-1. Moreover, the OAc^- anion also shows a similar trend, but a mild spectral change, with K_b calculated to be 2170 M^-1. Unlike those of CN^- and OAc^-, the addition of F^-, Cl^-, Br^-, and I^- anions causes a less pronounced spectral change with an isosbestic point at ca. 350 nm and K_b calculated to be 2863-750 M^-1. However, almost no spectral change can be observed for other anions (i.e., PF₆^-, NO₃^-, H₂PO₄^-, and ClO₄^-). Interestingly, the molecular loops of [Re(CO)₃Cl(Py₂S₂)]₂ (2; Py₂S₂ = 4,4'-dipyridyl disulfide) and [Re(CO)₃Cl(Py₂S)_0.35(Py₂S₂)_0.65]₂ (3; Py₂S = 4,4'-dipyridyl sulfide) can be isolated and structurally characterized by X-ray diffraction, where those crystals were grown from diethyl ether diffusion into a methanolic solution of complex 1 with [Bu₄N]CN and [Bu₄N]NO₃, respectively. It is noted that such unusual ligand-coupling reactions toward the homoligand and hybrid-ligand loops of complexes 2 and 3 can be achieved at room temperature in this study.