Tunable double photochromism of a family of bis-DTE bipyridine ligands and their dipolar Zn complexes. - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2012

Tunable double photochromism of a family of bis-DTE bipyridine ligands and their dipolar Zn complexes.

Résumé

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 L(a-d) (o,o) (a, D = H; b, D = OMe; c, D = NMe(2); d, D = NBu(2)) and/or the Lewis character of the metal ion center L(a-d)ZnX(2) (o,o) (L(a-c), X = OAc; L(d), 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 L(d)ZnCl(2) 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.
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Dates et versions

hal-00831009 , version 1 (09-09-2013)

Identifiants

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Lucie Ordronneau, Vincent Aubert, Rémi Métivier, Eléna Ishow, Julien Boixel, et al.. Tunable double photochromism of a family of bis-DTE bipyridine ligands and their dipolar Zn complexes.. Physical Chemistry Chemical Physics, 2012, 14 (8), pp.2599-605. ⟨10.1039/c2cp23333a⟩. ⟨hal-00831009⟩
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