Temperature-controlled formation of Anderson-type compounds and their conversion to [γ-Mo8O26]4−-based variants using pendent ligands

Abstract

Abstract By tuning the reaction temperature, two Anderson- and two [γ-Mo8O26]4−-based compounds decorated by pendent organic ligands, [CuII 9(bpz)2(pz)2(H2O)24][H2(Cr(OH)5Mo6O19)4]·11H2O (1), [CuII(bpz)2(H2O)2(γ-H4Mo8O26)]·2H2O (2), [CuII 2(tea)2(H2O)6(HCr(OH)6Mo6O18)2]· 6H2O (3) and [AgI(bpz)(H2O)(γ-H4Mo8O26)0.5] (4) (bpz=4-butyl-1H-pyrazole, pz=1H-pyrazole, tea=2-[1,2,4]triazol-4-yl-ethylamine), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, IR spectra and elemental analyses. In compound 1, there are two kinds of tri-nuclear CuII clusters induced by bpz and pz ligands, respectively. Four Anderson-type anions are linked by these tri-nuclear clusters to form a “W”-type subunit. In compound 2, the [Cu(bpz)2(H2O)2]2+ subunits connect the γ-Mo8 anions to construct a chain. The remaining two non-coordinated N donors in [Cu(bpz)2(H2O)2]2+ further link two adjacent γ-Mo8 anions through Mo–N bonds. In compound 3, there exists a bi-nuclear CuII cluster [Cu2(tea)2(H2O)6]4+. The discrete bi-nuclear CuII clusters and the CrMo6 anions link each other through abundant hydrogen bonding interactions. In compound 4, the [Ag(bpz)(H2O)]+ subunits connect γ-Mo8 anions to build a zigzag chain. The chains are further fused by other [Ag(bpz)(H2O)]+ cations to form a grid-like layer. There still exist Mo–N bonds in 4. We also have investigated the electrochemical and photocatalytic properties of 1–4.