Ni_(4)-thiacalix[4]arene sandwiched Mo_8 polyoxometalate bimetallic nanoclusters for electrocatalytic glucose oxidation

Available online two new Ni_(8)Mo_(8) bimetallic coordination clusters,[Ni_(4)(TC4A)]_(2)[(Mo_5~VMo_(3)~ⅥO_(24))(PO_(4))](+Solvent)(Ni_(8)PMo_(8),H_(4)TC4A=p-tert-butylthiacalix[4]arene) and[Ni_(4)(TC4A)]_(2)[(Mo_5~VMo_(3)~ⅥO_(24))(OH)(CO_(3))](+Solvent)(Ni_(8)Mo_(8)),were synthesized by solvothermal method and structurally characterized by single-crystal X-ray diffraction,powder X-ray diffraction,FT-IR spectroscopy,and TGA experiments,respectively.The usage of H_(3)PMo_(12)O_(40) as source for Ni_(8)PMo_(8) resulted a sandwich like structure built from two Ni_(4)-thiacalix[4]arene units and a Mo_(8) polyoxometalate with inner spaces of PO_(4)^(3-).Ni_(8)Mo_(8) with the similar structure to that of Ni_(8)PMo_(8) is from H_(2)MoO_(4) starting reagent with OH^(-)and CO_(3)^(2-)anions encapsulated in the center.The two clusters can be directly loaded on carbon paper and utilized as working electrodes which showed distinguishable performances for glucose detection and oxidation.This work provides a better understanding of the structure-property relationships in using substituted polyoxometalates for electrochemical applications and is helpful for building calixarene-based or polyoxometalatebased functional materials.