Structure-Activated Copper Photosensitisers for Photocatalytic Water Reduction.

A series of phenanthroline-based ligands have been synthesised and their influence as bidentate nitrogen ligands in heteroleptic [Cu(P^P)(N^N)] photosensitisers in light-driven water reduction has been studied. In this noble-metal-free Cu-Fe-based photocatalytic water reduction system, the structural effects of the nitrogen ligands have been explored, including the steric and electronic effects of substituents at the 2,9- and 4,7-positions of phenanthroline. Ligands were prepared that led to increased hydrogen generation, with turnover numbers (TON ) of up to 1388 being observed.

Solvothermal synthesis of four polyoxometalate-based coordination polymers including diverse Ag(I)···π interactions.

Four 3D POM-based silver coordination polymers, namely, [Ag17(ptz)11(PW12O40)2]n (1), [Ag17(ptz)11(PMo12O40)2]n (2), [Ag12(ptz)6(CN)2(SiW12O40)]n (3), and [Ag19(ptz)8(H2ptz)(H3ptz)(AgP5W30O110)·7H2O]n (4), have been obtained by solvothermal reaction of AgNO3 and 5-phenyl-1H-tetrazole (Hptz) ligand in the presence of four types of polyoxometalates. Structural analysis shows that four types of Ag(I)···π interactions, m-η(1), m/p-η(2), o/m-η(2), and o/m/p-η(3), were observed in compounds 1-4, depending on the polyoxometalates used. The in situ generated CN(-) ion in compound 3 shows unprecedented mixed σ and π bonding modes, similar to the C2(2-) ion in well-studied silver acetylides.

Two triazole-based metal-organic frameworks constructed from nanosized Cu20 and Cu30 wheels.

Two metal-organic frameworks constructed from nanosized Cu(20) and Cu(30) wheels have been obtained under hydrothermal conditions based on 1,2,3-triazole and 1-H-1,2,3-benzotriazole, respectively. Crystal structure analysis shows that their differences in the size and nuclearity of Cu(20) and Cu(30) wheels are attributed to the steric effect of ligands.