Hybrid compounds assembled from copper-triazole complexes and phosphomolybdic acid as advanced catalysts for the oxidation of olefins with oxygenElectronic supplementary information (ESI) available: Detailed Experimental section, figures, TG curves, together with tables. CCDC 1555147 (1) and 1555148 (2). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7dt03198j

Two hybrid compounds, namely [Cu I 4 (3atrz) 4 ][PMo VI 11 Mo V O 40 ] ( 1 ) and [Cu I 6 (3atrz) 6 ][PMo 12 O 40 ] 2 ( 2 ), were synthesized through hydrothermal reactions of 3-amino-1,2,4-triazole (3atrz), phosphomolybdic acid (PMA) and appropriate copper salts. Crystal structure analysis reveals that compound 1 contains one-dimensional Cu-3atrz chains. The unit of compound 2 contains a double calyx[3]arene-shaped hexamer, which is composed of six two-coordinated Cu I atoms and six 3atrz ligands. Both compounds 1 and 2 present a three-dimensional hybrid structure, which is built by the self-assembly of Cu-3atrz clusters and Keggin-type PMA units. The resulting hybrid compounds can act as highly efficient heterogeneous catalysts for the selective oxidation of olefins with molecular oxygen as the oxidant in the presence of a trace amount of tert -butyl hydroperoxide ( t -BuOOH). Their excellent catalytic properties can be mainly attributed to the existence of stabilized Cu I complexes with an appropriate chemical environment and a spacious structure, which can interact with t -BuOOH to form catalytic sites for the direct activation of O 2 . This work demonstrates that the hybrid compounds assembled from copper-3atrz complexes and phosphomolybdic acid may have great potential in molecular O 2 -mediated catalytic oxidation reactions, which can certainly build a platform for deep insight into the biologically relevant catalytic oxidation processes. Hybrid compounds of [Cu I 4 (3atrz) 4 ][PMo VI 11 Mo V O 40 ] ( 1 ) and [Cu I 6 (3atrz) 6 ][PMo 12 O 40 ] 2 ( 2 ) are active catalysts for olefin oxidation.