화학공학소재연구정보센터
Inorganic Chemistry, Vol.56, No.22, 13822-13828, 2017
Organoarsonate Functionalization of Heteropolyoxotungstates
Functionalization of the {P8W48} polyoxotungstate (POT) archetype with aromatic organoarsonates results in the first homometallic {P8W48} derivatives, with the general formula [((RAsO)-O-V)(4)(PV8W48O184)-O-VI](32-) [R = C6H5 (1) or p-(H2N)C6H4 (2)]. Short As-O bonds here induce unusual bending of the otherwise rigid {P8W48} macrocycle, breaking its D-4h symmetry. The obtained species also represent the first lacunary POTs functionalized with organoarsonates and can potentially act as polyoxometalate precursors themselves. We elaborate solution stability in different aqueous media using H-1 and P-31 NMR spectroscopy and possible pathways for subsequent transformations in aqueous solutions of the functionalized polyanions. Recrystallization of the K+/Li+/dimethylammonium salt of 2 from 4 M LiCl solution yielded a further functionalized POT, [(H3NC6H4AsO)(3)P8W48O184Hx{WO2(H2O)(2)}0.4]((30.2-x)-) (3), revealing dissociation of the organoarsonate fragments in slightly acidic aqueous solutions followed by their rearrangement within the inner POT cavity