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.