Solid state coordination chemistry of metal oxides: Structural consequences of fluoride incorporation into the oxovanadium-copper-bisterpy-{O3P(CH2)nPO 3}4- system, n = 1-5 (bisterpy = 2,2′:4′,4″:2″,2‴-quaterpyridyl-6′, 6″-di-2-pyridine)

Wayne Ouellette, Vladimir Golub, Charles J. O'Connor, Jon A Zubieta

Research output: Contribution to journalArticle

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Abstract

Hydrothermal reactions of a vanadate source, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H2O3P(CH 2)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{HO 3PCH2PO3}{O3PCH2PO 3}] (1) and [{Cu2(bisterpy)}-V2F 4O4{HO3P(CH2)2PO 3H}] (3), the two-dimensional [{Cu2(bisterpy)}V 2F2O2(H2O)2{HO 3P(CH2)2PO3} 2]·2H2O (2-2H2O), [{Cu 2(bisterpy)(H2O)2}V2F 2O2{O3P(CH2)3PO 3}{HO3P(CH2)3PO3H} (4) and [{Cu2(bisterpy)}V4F4O 4-(OH)(H2O){HO3P(CH2) 5PO3}{O3P(CH2)5PO 3}]· H2O (9·H2O) and the three-dimensional [{Cu2(bisterpy)}3V8F 6O17-{HO3P(CH2)3PO 3}4]·0.8H2O (5·0.8H 2O), [{Cu2(bisterpy)}V4F2O 6{O3P(CH2)4PO3} 2] (8) and [{Cu2(bisterpy)(H2O)} 2-V8F4O3(OH)4{HO 3P(CH2)5PO3H}2{O 3P(CH2)5PO3}3]·4.8H 2O (10·4.8H2O). In addition, two members of the oxovanadium/Cu2(bisterpy)/organodiphosphonate family [{Cu 2(bisterpy)}V2O4{HO3P(CH 2)3PO3}2] (6) and [{Cu 2(bisterpy)}3V4O3(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/Cu 2(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.

Original languageEnglish (US)
Pages (from-to)291-309
Number of pages19
JournalDalton Transactions
Issue number2
DOIs
StatePublished - Jan 21 2005

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