Syntheses, structures, and steady state and time resolved photophysical properties of a tetraiminodiphenol macrocyclic ligand and its dinuclear zinc(II)/cadmium(II) complexes with coordinating and noncoordinating anions

摘要

The work in the present investigation reports the syntheses, structures, steady state, and time-resolved photophysical properties of a tetraiminodiphenol macrocyclic ligand H _2L and its eight dinuclear zinc(II) complexes and one cadmium(II) complex having composition [Zn 2L(H _2O) _2](ClO _4) _2·2CH _3CN (1), [Zn _2L(H _2O) _2](ClO _4) _2·2dmf (2), [Zn _2L(H _2O) _2](NO _3) 2·2dmf (3), [Zn _2LCl _2] (4), [Zn _2L(N _3) _2] (5), [Zn _2L(NCS) _2] (6), [Zn _2L(NCO) _2] (7), [Zn _2L(NCSe) _2] 2·dmf (8), and [Cd _2L(OAc) _2] (9) with various coordinating and noncoordinating anions. The structures of all the complexes 1-9 have been determined by single-crystal X-ray diffraction. The noncovalent interactions in the complexes result in the generation of the following topologies: two-dimensional network in 1, 2, 4, 6, 7, 8, and 9; three-dimensional network in 5. Spectrophotometric and spectrofluorometric titrations of the diprotonated salt [H _4L](ClO _4) _2 with triethylamine as well as with zinc(II) acetate and cadmium(II) acetate have been carried out, revealing fluorescence enhancement of the macrocyclic system by the base and the metal ions. Steady state fluorescence properties of [H _4L](ClO _4) _2 and 1-9 have been studied and their quantum yields have been determined. Time resolved fluorescence behavior of [H _4L](ClO _4) _2 and the dizinc(II) and dicadmium(II) complexes 1-9 have also been studied, and their lifetimes and radiative and nonradiative rate constants have been determined. The induced fluorescence enhancement of the macrocycle by zinc(II) and cadmium(II) is in line with the greater rate of increase of the radiative rate constants in comparison to the smaller rate of increase of nonradiative rate constants for the metal complexes. The fluorescence decay profiles of all the systems, being investigated here, that is, [H _4L](ClO _4) _2 and 1-9, follow triexponential patterns, revealing that at least three conformers/components are responsible to exhibit the fluorescence decay behavior. The systems and studies in this report have been compared with those in the reports of the previously published similar systems, revealing some interesting aspects.