Nanocrystalline hybrid inorganic–organic one-dimensional chain systems tailored with 2- and 3-phenyl ring monocarboxylic acids

Abstract

Two novel nanosized hybrid inorganic–organic frameworks, VO(C₁₄H₉COO)₂, and VO(C₁₀H₇COO)₂ have been solvothermally synthesized and their structures elucidated using a combination of powder XRD and DFT geometry optimization. They contain one-dimensional chains of corner-sharing tetrahedra in the case of VO(C₁₀H₇COO)₂, and corner-sharing octahedra for VO(C₁₄H₉COO)₂ oriented along orthorhombic/monoclinic c-axis, respectively. While VO(C₁₄H₉COO)₂ exhibits bidentate bridging binding of organic moiety to the metal center, VO(C₁₀H₇COO)₂ shows a monodentate mode as evidenced from DFT and infrared spectroscopy. Both hybrids exhibit fiber-like morphology, consisting of smaller individual single crystals aligned in parallel to the growth direction along the c-axis. They are thermally stable up to 350 °C having even more stable impurities containing vanadium in its highest oxidation state. The magnetic properties have also been investigated and indicate antiferromagnetic ordering along the chains characterized by rather low spin exchange parameters.