Redox-controlled helical self-assembly of a polyoxometalate complex

摘要

Polyoxometalate (POM) complex (DODA)_2[Mo_6O _(19)] with a symmetrical linear structure was prepared conveniently by replacing the tetrabutylammonium (TBA) counterions of Lindquist-type cluster (TBA)_2[Mo_6O_(19)] with cationic surfactant dioctadecyldimethylammonium (DODA). A helical self-assembled structure of the complex was formed in dichloromethane/propanol. The dynamically reversible transformation between helical and spherical assemblies on alternate UV irradiation and H_2O_2 oxidation was characterized by SEM, TEM, and UV/Vis studies. The redox-controlled morphology change is modulated by variation of the electrostatic interactions between the inorganic polyanion and the organic cation DODA through controlling the redox properties of the POM component, as shown by the XRD, X-ray photoelectron spectroscopic, and ~1H NMR measurements. The strategy applied herein is a unique example of targeted smart and helical assembly of POM complexes. Smart helical assembly: A symmetrical helical assembly was constructed from surfactant-enwrapped Lindqvist polyoxometalate (POM) complex (DODA)_2[Mo_6O _(19)] (DODA=dioctadecyldimethylammonium). Reversible smart transformation between helical and spherical assemblies associated with photochromism was achieved by controlling the redox properties of the POM component through UV irradiative reduction and H_2O_2 oxidation (see figure).