Photophysical, electrochemical and electrochromic properties of copper-bis(4,4′-dimethyl-6,6′-diphenyl-2,2′-bipyridine) complexes

摘要

The synthesis, solution and solid state structural characterization, photophysical and electrochemical properties of two redox forms of an electrochromic copper-bis(4,4′-dimethyl-6,6′-diphenyl-2,2′-bipyridine) complex, [Cu(3)_2]~n (n= +1, +2), are presented. Both complexes were characterized in the solid state by X-ray diffraction methods on single-crystals showing that both forms exist in a pseudo-tetrahedral coordination, and a comparison with other structures was made. Like most copper(Ⅰ) complexes, the red [Cu(3)_2]~+ complex shows a rather weak emission (Φ_(em) = 2.7 x 10~(-4), dichloromethane). The lifetime of the emitting MLCT state is 34 +- 1 ns, as observed with time resolved emission, and transient absorption (in deoxygenated dichloromethane). Typical emission and transient absorption spectra are presented. The transient absorption spectra indicate that the MLCT state absorbs stronger than the ground state, which is relatively uncommon for metal bipyridine complexes, i.e. no ground state bleaching is observed. The green [(3)_2Cu]~(2+) complex does not show any observable emission or transient absorption, which is a common feature for Cu(Ⅱ) complexes of this type. The electronic absorption spectra of the chemically and electrochemically produced copper(Ⅰ/Ⅱ) complexes are identical. The repeated electrochemical conversion of the Cu(Ⅰ) center into Cu(Ⅱ) and vice versa does not cause any decomposition. This is consistent with a fully reversible Cu(Ⅰ)/Cu(Ⅱ) redox couple in the corresponding cyclic voltammogram, (E_(1/2) (Cu(Ⅰ)/Cu(Ⅱ)) = + 0.68 V vs. SCE= + 0.23 V vs. Fc/Fc~+). These observations indicate that no large structural reorganization occurs upon electrochemical timescales (sub second), and that the different ways of generating the complexes does not effect their final structure, apart from the small differences observed in the X-ray structures of both forms. These characteristics make these complexes rather well suited for their incorporation into an electrochromic display configuration.