Engineering Multifunctionality in Hybrid Polyoxometalates: Aromatic Sulfonium Octamolybdates as Excellent Photochromic Materials and Self-Separating Catalysts for Epoxidation.

Engineering multifunctionality in hybrid polyoxometalates (hybrid POMs) is an interesting but scarcely explored topic. Herein, we set about engineering two important materials properties, viz., photochromism and self-separating catalysis, in a hybrid POM by modulating the counterion motif. A series of six aromatic sulfonium counterions have been developed on the basis of an aromatic sulfonium counterion motif that allows structural and electronic fine-tuning by changing substituents at multiple locations. Using the aromatic sulfonium counterions and sodium molybdate, six new aromatic sulfonium octamolybdate hybrids (1-6) having formulas (HPDS)4 [Mo8 O26 ] (1), (HMPDS)4 [Mo8 O26 ] (2), (MPDS)4 [Mo8 O26 ] (3), (APDS)4 [Mo8 O26 ] (4), (AMPDS)4 [Mo8 O26 ] (5), and (MAPDS)4 [Mo8 O26 ] (6) (where HPDS = (4-hydroxyphenyl)dimethylsulfonium, HMPDS = (4-hydroxy-2-methylphenyl)dimethylsulfonium, MPDS = (4-methoxyphenyl)dimethylsulfonium, APDS = (4-(allyloxy)phenyl)dimethylsulfonium, AMPDS = (4-(allyloxy)-2-methylphenyl)dimethylsulfonium and MAPDS = (4(methacryloyloxy)phenyl)dimethylsulfonium) have been synthesized, and their structures were confirmed by single crystal X-ray diffraction and ESI-MS analyses. Hybrids 1-6 acted as good solid-state photochromic materials exhibiting color change from white to purple under UV illumination (350 nm), and we show here that the photochromic properties of hybrids 1-6 could be modulated by changing the substitutions on the counterion motif. A coloration kinetic half-life (t1/2 ) of 0.33 min was achieved with this class of hybrid POMs. Hybrids 1-6 exhibited excellent self-separating catalytic properties toward the epoxidation of olefins, yielding up to 99% epoxide product with good selectivity in short time. The substituents on the aromatic sulfonium counterions helps to fine-tune the electronic, lipophilic, and solubility properties of the hybrids and thereby their catalytic properties. Moreover, we used ESI-MS analyses to understand the mechanism of catalysis exhibited by octamolybdates 1-6 in the presence of H2 O2 , and we succeeded in identifying a hitherto undetected intermediate, tetraperoxo-octamolybdates, shedding more light on the epoxidation mechanism.