Solid state coordination chemistry of metal oxides: structural consequences of fluoride incorporation into the oxovanadium–copper–bisterpy–{O3P(CH2)nPO3}4− system, n = 1–5 (bisterpy = 2,2′:4′,4″:2″,2‴-quaterpyridyl-6′,6″-di-2-pyridine)

Abstract

Hydrothermal reactions of a vanadate source, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H₂O₃P(CH₂)_nPO₃H₂ (n = 1–5), in the presence of HF, yielded a family of materials of the type oxyfluorovanadium/copper–bisterpy/organodiphosphonate. Under similar reaction conditions, variations in diphosphonate tether length n provided the one-dimensional [{Cu₂(bisterpy)}V₂F₂O₂{HO₃PCH₂PO₃}{O₃PCH₂PO₃}] (1) and [{Cu₂(bisterpy)}V₂F₄O₄{HO₃P(CH₂)₂PO₃H}] (3), the two-dimensional [{Cu₂(bisterpy)}V₂F₂O₂(H₂O)₂{HO₃P(CH₂)₂PO₃}₂]·2H₂O (2·2H₂O), [{Cu₂(bisterpy)(H₂O)₂}V₂F₂O₂{O₃P(CH₂)₃PO₃}{HO₃P(CH₂)₃PO₃H} (4) and [{Cu₂(bisterpy)}V₄F₄O₄(OH)(H₂O){HO₃P(CH₂)₅PO₃}{O₃P(CH₂)₅PO₃}]·H₂O (9·H₂O) and the three-dimensional [{Cu₂(bisterpy)}₃V₈F₆O₁₇{HO₃P(CH₂)₃PO₃}₄]·0.8H₂O (5·0.8H₂O), [{Cu₂(bisterpy)}V₄F₂O₆{O₃P(CH₂)₄PO₃}₂] (8) and [{Cu₂(bisterpy)(H₂O)}₂V₈F₄O₈(OH)₄{HO₃P(CH₂)₅PO₃H}₂{O₃P(CH₂)₅PO₃}₃]·4.8H₂O (10·4.8H₂O). In addition, two members of the oxovanadium/Cu₂(bisterpy)/organodiphosphonate family [{Cu₂(bisterpy)}V₂O₄{HO₃P(CH₂)₃PO₃}₂] (6) and [{Cu₂(bisterpy)}₃V₄O₈(OH)₂{O₃P(CH₂)₃PO₃}₂{HO₃P(CH₂)₃PO₃}₂]·5H₂O (7·5H₂O) cocrystallized from the reaction mixture which provided 5. The overall architectures reveal embedded substructures based on V/P/O(F) clusters, chains, networks, and frameworks. In contrast to the oxovanadium/Cu₂(bisterpy)/ organodiphosphonate family, several of the materials of this study also exhibit the direct condensation of vanadium polyhedra to produce binuclear and/or tetranuclear building units.