Vanadyl sulfates:molecular structure, magnetism and electrochemical activity

Reaction of differing amounts of vanadyl sulfate with p-tert-butylthiacalix[4]areneH4 and base allows access to the vanadyl-sulfate species [NEt4]4[(VO)4(3-OH)4(SO4)4]∙1/2H2O (1), [HNEt3]5[(VO)5(3-O)4(SO4)4]∙4MeCN (2∙4MeCN) and [NEt4]2[(VO)6(O)2(SO4)4(OMe)(OH2)]∙MeCN (3∙MeCN). Similar use of p-tert-butylsulfonylcalix[4]areneH4, p-tert-butylcalix[8]areneH8 or p-tert-butylhexahomotrioxacalix[3]areneH3 led to the isolation of [HNEt3]2[H2NEt2]2[VO(OMe)]2p-tert-butylcalix[8-SO2]areneH2] (4), [HNEt3]2[V(O)2p-tert-butylcalix[8]areneH5] (5) and [HNEt3]2[VIV2VV4O11(OMe)8] (6), respectively. Dc magnetic susceptibility measurements were performed on powdered microcrystalline samples of 1-3 in the T = 300 - 2 K temperature range. Preliminary screening for electrochemical water oxidation revealed some activity for 2 with turnover frequency (TOF) and number (TON) of 2.2 × 10-4 s-1 and 6.44 × 10-6 (mmol O2 / mmol cat.), respectively. The compound 3 showed an improved electrochemical activity in the presence of water. This is related to the increased number and the rate of electrons exchanged during oxidation of V4+ species, facilitated by protons generated in the water discharge process

Syntheses and ligand interconversions of copper(II) derivatives of the metalloligand [Pt 2(μ-S) 2(PPh 3) 4]

10.1039/b505648aDalton Transactions162780-278