Solvatothermal chemistry of organically-templated vanadium fluorides and oxyfluorides

Abstract

The solvatothermal reactions of V 2O 5, the appropriate organoamine and HF in the temperature range 100–180 °C yielded a series of vanadium fluorides and oxyfluorides. The compounds [NH 4][H 3N(CH 2) 2NH 3][VF 6] ( 1) and [H 3N(CH 2) 2NH 3][VF 5(H 2O)] ( 2) contain mononuclear V(III) anions, while [H 3N(CH 2) 2NH 2(CH 2) 2NH 3] 2 [VF 5(H 2O)] 2[VOF 4(H 2O)] ( 3) exhibits both V(IV) and V(III) mononuclear anions. Both compound 4, [H 3NCH 2(C 6H 4)CH 2NH 3][VOF 4]·H 2O ( 4·H 2O) and compound 5, [HN(C 2H 4) 3NH][V 2O 2F 6 (H 2O) 2] ( 5) contain binuclear anions constructed from edge-sharing V(IV) octahedra. In contrast, [H 3N(CH 2) 2NH 2(CH 2) 2NH 3] 2[V 4O 4F 14(H 2O) 2], ( 6) exhibits a tetranuclear unit of edge- and corner-sharing V(IV) octahedra. Compound 7, [H 3N(CH 2) 2NH 2][VF 5], contains chains of corner-sharing {V IVF 6} octahedra, while [H 2N(C 2H 4) 2NH 2] 3[V 4F 17O]·1.5H 2O ( 8·1.5H 2O) is two-dimensional with a layer of V(III) and V(IV) octahedra in an edge- and corner-sharing arrangement. In the case of [H 3N(CH 2) 2NH 3][V 2O 6] ( 9), there was no fluoride incorporation, and the { V 2 O 6 } n 2 n - anion is a one-dimensional chain of corner-sharing V(V) tetrahedra.