Five-coordinate geometry around ruthenium with highly exposed active sites have attracted intensive scientific interests due to their superior properties and extensive applications. Herein, we report a series of structurally controllable...

Two new Silverton archetypes [NaM12O42]11− were demonstrated in the POMs Na3[NaM12O42(Ru(DMSO)3)4]·13H2O (M = Mo, W). The alkali metal Na+ ion incubated as a heteroatom is reported for the first time in POMs and further certified by 23Na NMR.

A 1-D infinite helical chain-like organic-inorganic hybrid arsenotungstate NaH[{Pr(HO)}{AsWO}{WO(mal)}]·24HO (mal = malate) (1) was prepared, which was characterized by elemental analyses, thermogravimetric (TG) analyses, IR spectroscopy, powder X-ray diffraction (PXRD) and X-ray single-crystal diffraction. Structural characterization revealed that 1 comprises the organo-functionalized [{AsWO}{WO(mal)}] polyanions hinged together by the Pr ions forming a 1-D infinite helical chain-like architecture. The malate ligand may play a vital role to stabilize the structure of 1 by the formation of the five-membered W-O-C-C-O chelate ring. Solid state photoluminescence reveals that 1 features excitation wavelength-dependent emission properties, achieving a reversible emission color switching simply via changing the excitation wavelength. Time-resolved emission spectroscopy (TRES) indicates that the photoexcitation O → M ligand to metal charge transfer (LMCT) of arsenotungstate fragments can sensitize the Pr ions through intramolecular energy transitions in 1.