Multifunctional Aryl Sulfonium Decavanadates: Tuning the Photochromic and Heterogeneous Oxidative Desulfurization Catalytic Properties Using Salicylaldehyde-type Functional Moieties on Counterions.

Abstract

Multifunctional materials based on polyoxovanadates (POVs) have rarely been reported. Herein, we used aryl sulfonium counterions (ASCIs) bearing a salicylaldehyde-type functionality to tune the properties of decavanadate ([V10O28]6-)-based hybrids for their application in photochromism and heterogeneous oxidative desulfurization (ODS) catalysis. The counterions FHPDS ((3-formyl-4-hydroxyphenyl)dimethylsulfonium), DFHPDS ((3,5-diformyl-4-hydroxyphenyl)dimethylsulfonium), and EFPDS ((4-ethoxy-3-formylphenyl)dimethylsulfonium) were clubbed with the decavanadate cluster to generate the hybrids (FHPDS)4[H2V10O28](H2O)4 (HY1), (DFHPDS)4[H2V10O28](H2O)3 (HY2), and (EFPDS)4[H2V10O28](H2O)6 (HY3). The photochromic properties of these hybrids were tested under 365 nm irradiation, which showed a color change from yellow to green. Different hybrids exhibited different photocoloration half-life (t1/2) values in the range of 0.77-28.38 min, suggesting the dependence of the photocoloration properties upon functional groups on the counterions. The hybrid HY2, having a 2,6-diformyl phenol moiety on the ASCI, exhibited an impressive t1/2 of 0.77 min. UP to 70% reversibility of photocoloration was achieved for the best photochromic hybrid HY2 in 48 h at 70 °C under an oxygen atmosphere. Theoretical and experimental data suggested that some of these aryl sulfonium POVs follow a different e--h+ stabilization mechanism than traditional sulfonium POM hybrids. Further, the salicylaldehyde-type ASCIs control the solubility of the decavanadate hybrids, which enables their application as heterogeneous catalysts for the selective oxidation of various sulfides. The nature of the substituents on the ASCIs also affected their catalytic activities; the counterion that facilitates the reversible V4+/V5+ switching enhances the catalytic ODS efficiency of the hybrids. Using HY2 as the catalyst, up to 99% conversion and 96% selectivity toward sulfones were achieved in dibenzothiophene (DBT) oxidation. The present study suggests a new promising approach for controlling POVs' photoresponsive and catalytic properties by using ASCIs bearing salicylaldehyde-type functional moieties.