Syntheses,Structures And Properties Of Polyoxometalates-based Copper(?)Complexes Of A Resorcin[4]Arene Derivative

In this paper,a new resorcin[4]arene ligand(L)was designed and synthesized based on pyrimidine group.By applying a newly designed resorcin[4]arene ligand,three Keggin POMs-based complexes were sucessfully synthesized under solvothermal condition,namely,[CuI6Br3L3(PMO12O40)]·8H2O(1),[Cu16Cl3L3(PW12O40)]·8H2O(2)and[CUI4Cl2L3(H2SiW12O40)]·8H2O 4EtOH(3).The frameworks of complexes 1-3 are formed by Cu(I)linking with Keggin-type polyacids and L ligands.In 1 and 2,the N atoms in the L ligands and the terminal O in the polyacids formed an unique propeller trimer through the Cu(I)metal cation.The trimers are connected by weak C-H…O bonds to form a two-dimensional network.In 3,the L ligand,the polyacid and the Cu(I)metal cation formed a layered structure.Strikingly,1-3 are highly stable in aqueous solutions of wide pH range of 1-14 and various organic solvents.Considering that the complex contains both Cu(I)active sites and polyacids,1 as a recycling catalyst features excellent catalytic activities for oxidation desulfurization reactions and azide-alkyne cycloaddition reaction.Moreover,the electrocatalytic activities for the oxidation of ascorbic acid and reduction of NaBrO3 were also investigated by using 1 as a bifunctional electrocatalyst.