Design, synthesis, photophysics, and anion-binding studies of bis(dicyclohexylphosphino)methane-containing dinuclear gold(I) thiolate complexes with urea receptors

摘要

A series of bis(dicyclohexylphosphino)methane (dcpm)-containing gold(I) thiolate complexes with urea receptors, 1-3, has been successfully designed and synthesized, and their photophysical and anion-binding properties have been studied. The linker between the thiolate and the urea group, and the electronic environment of the urea moiety, have been found to exert a great influence on the photophysical and anion-binding properties of the complexes. Complex 3 displays an intense long-lived orange-red luminescence at around 620 nm in the solid state and in the glass state at 77 K, which is considerably red shifted from the band seen in a solution of dichloromethane at room temperature, suggesting the presence of Au···Au interactions. Upon introducing an electronwithdrawing NO_2 group, complex 1 was found to show high selectivity and sensitivity for F~- through a drastic color change from yellow to red. The anionbinding constants of the complexes have been determined from electronic absorption and~1H NMR spectroscopy titration studies and the data were found to fit well to a 1:1 binding model for the interactions between the complexes and the anions. Complexes 1 and 2 show the same anion selectivity trend of F~- > AcO~- > H_2PO_4 > Cl~- ≈ Br~- ≈I ~-, which is consistent with the trend in anion basicity. In addition, complex 1 has been shown to exhibit higher binding affinity for anions compared with those of complexes 2 and 3, probably due to the higher acidity of the urea moiety as a result of the introduction of the NO_2 group.