Inorganic organic hybrids of phosphotungstate Keggin anion and a Schiff base cation

Abstract

We present two organic-inorganic hybrids [C9H9N4O]3[PW12O40]∙C9H8N4O∙4CH3OH (1) and [C9H9N4O]3[PW12O40]∙C9H8N4O (2) consisting of 4-(salicylideneamino)-1,2,4-triazole cations and Keggin type phosphotungstate anions. Compounds 1 and 2 are characterized by NMR, UV-Vis, IR spectroscopy, and single-crystal X-ray diffraction studies. The crystal structures of compounds 1 and 2 show additional organic Schiff base molecules as lattice components. The analysis of electron paramagnetic resonance (EPR) spectra of compounds 1 and 2 shows a peak at a g-value of 2.0023, characteristic of a free radical species. The attempted spin-trapping reaction of compound 2 with C9H18NO [2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)] resulted in the formation of single crystals of [C9H18NO]3 [PW12O40] (3) consisting of TEMPOnium cation and phosphotungstate anion. Finally, compound 2 has been used as a radical initiator for free radical polymerization of styrene to polystyrene.