Hydrothermal synthesis, crystal structure and properties of a 3D-framework polyoxometalate assembly: [Ag(4,4′-bipy)](OH){[Ag(4,4′-bipy)]2[PAgW12O40]}·3.5H2O

A 3D framework assembly based on the Keggin tungstophosphate POM with silver (I) transition metal and N-ligand organic moiety and of formula [Ag(4,4′-bipy)](OH){[Ag(4,4′-bipy)]2[PAgW12O40]}·3.5H2O (1) (bipy=bipyridine) has been synthesized by hydrothermal method and structurally characterized. The crystal of 1 belongs to triclinic, space group P  -1, Mr=3857.27Mr=3857.27, a=10.2741(3)Å, b=11.3723(4)Å, c=14.0161(5)Å, α=85.7249(5)°α=85.7249(5)°, β=72.8795(5)°β=72.8795(5)°, γ=79.9543(5)°γ=79.9543(5)°, V=1540.61(9)Å3, Z=1Z=1, Dcalc=4.158Mgm-3. The final statistics based on F2 are GOF=1.045, R1=0.0326R1=0.0326 and wR2=0.0843wR2=0.0843 for I>2σ(I)I>2σ(I). X-ray diffraction analysis revealed that the molecular structure of 1 consists of a neutral fragment {[AgI(4,4′-bipy)]2[PAgIWVI12O40]}, [AgI(4,4′-bipy)]+ cation, hydroxide anion and lattice water molecules. The {[AgI(4,4′-bipy)]2[PAgIWVI12O40]} subunits are interconnected through Ag(I) with bipyridine ligands, both surface bridging and terminal oxygen atoms of polyoxoanions (POMs) to represent a novel three-dimensional (3D) polymer with 1D elliptic channels. Meanwhile, the [AgI(4,4′-bipy)]+ cations are also linked each other to form 1D chains, and embedded in 1D elliptic channels.

Graphical abstractA 3D framework assembly based on the Keggin tungstophosphate polyoxoanion (POM) with silver (I) transition metal and N-ligand organic moiety and of formula [Ag(4,4′-bipy)](OH){[Ag(4,4′-bipy)]2[PAgW12O40]}·3.5H2O (1) (bipy=bipyridine) has been synthesized by hydrothermal method and structurally characterized. The molecular structure of 1 consists of a neutral fragment {[AgI(4,4′-bipy)]2[PAgIWVI12O40]}, [AgI(4,4′-bipy)]+ cation, oxyhydrogen anion and lattice water molecules. The {[AgI(4,4′-bipy)]2[PAgIWVI12O40]} subunits are interconnected through Ag(I) with bipyridine ligands, both surface bridging and terminal oxygen atoms of POMs to represent a novel 3D polymer with 1D elliptic channels. Meanwhile, the [AgI(4,4′-bipy)]+ cations are also linked each other to form 1D chains, and embedded in 1D elliptic channels.Figure optionsDownload full-size imageDownload as PowerPoint slide