Solvothermal Syntheses and Structure of a New Polyoxomolybdate Functionalized with Carboxyphosphonate

Abstract A new functionalized polyoxomolybdate [(HOOCC 5 H 9 NCH 2 PO 3 ) 2 Mo 5 O 15 ] 4– ( 1 ) was synthesized by solvothermal reaction at 120 °C and structurally characterized by X‐ray single‐crystal diffraction, X‐ray powder diffraction as well as with infrared spectroscopy, elemental analysis, and thermogravimetric analysis. The title polyoxoanion consists of a ring of five distorted MoO 6 octahedra linked through four edge‐sharing and one corner‐sharing junctions. Two pending carboxyphosphonate ligands are attached on opposite sides of the ring by the two PO 3 groups. As a result the two dangling arms with their terminal carboxylate groups protrude away from the {Mo 5 O 15 } framework in diametrically opposed directions. Each Mo 5 ‐ring is further connected to adjacent Mo 5 ‐ring through hydrogen bonds, which consist in the protonated nitrogen atoms, the carboxyl oxygen atoms from L 3– ligands and oxygen atoms from {Mo 5 O 15 } cluster to form a 2D framework structure.