Tunable double photochromism of a family of bis-DTE bipyridineligands and their dipolar Zn complexes

The photoinduced ring-closure/ring-opening reactions of a series of bis-dithienylethene derivatives, as free ligands and Zn(II)-complexes, are investigated by resorting to theoretical (time-dependent density functional theory) and kinetic analyses in solution. The originality of the system stems from the tunability of the photoreaction quantum yields and conversion yields as a function of the electronic structure. The latter could be varied by modifying the electron-donating character of the DTE-end substituents La–da–d (o,o) (a, D = H; b, D = OMe; c, D = NMe2; d, D = NBu2) and/or the Lewis character of the metal ion center Laa––ddZnX2 (o,o) (La–ca–c, X = OAc; Lddd, X = Cl). The orbital description of the doubly-open form (o,o) and half-closed form (o,c) predicts that double closure to the form (c,c) would occur using UV irradiation. Photokinetic studies on the complete series demonstrate that photocyclization proceeds following a sequential ring closure mechanism. They clearly point out distinct quantum yields for the first and second ring closures, the latter being characterized by a significantly lower value. Dramatic decrease in both the quantum yields of the ring-closure and ring-opening processes is demonstrated for the complex LddZnCl22 exhibiting the strongest charge-transfer character in the series investigated. These studies show that this series of DTE derivatives provides an efficient strategy to tune the photochromic properties through the combination of the electron-donor and electron-acceptor (D–A) groups.