Two novel Krebs-type polyoxoanions [Cu I2(WO 2) 2(β-XW 9O 33) 2] 12− (X = Sb III, Bi III) resulting in 2D layer structures linked by copper(I) ions and copper(II) complex groups

Abstract

Two sandwich-type organic–inorganic hybrid polyoxotungstates [enH 2] 5[Cu II(en) 2][Cu I 2(WO 2) 2(β-SbW 9O 33) 2]·16H 2O ( 1) and [enH 2] 5[Cu II(en) 2][Cu I 2(WO 2) 2(β-BiW 9O 33) 2]·22H 2O ( 2) (en = ethylenediamine) have been synthesized hydrothermally and structurally characterized by elemental analyses, IR spectra, thermal stability analyses, X-ray powder diffraction, and single-crystal X-ray diffraction. The polyoxoanions in 1 and 2 are composed of two trivacant (B-β-XW 9O 33) 9− (X = Sb III ( 1), Bi III ( 2)) subunits joined together by two Cu(I) ions and two W(VI) ions resulting in two novel Krebs-type sandwich structures. These polyoxoanions are further connected by Cu(I) ions and [Cu II(en) 2] 2+ coordination cations, and afford the first copper(I)-linked 2D layer structure constructed from Krebs-type polyoxotungstates. Additionally, the electrochemical behavior and electrocatalysis of 1 and 2 modified carbon paste electrodes (CPEs) have been studied. The results indicate that they have good electrocatalytic activities toward the reduction of nitrite.