Syntheses, structural characterization and properties of transition metal complexes of 5,5′-(1,4-phenylene)bis(1H-tetrazole) (H2bdt), 5′,5′′-(1,1′-biphenyl)-4,4′-diylbis(1H-tetrazole) (H2dbdt) and 5,5′,5′′-(1,3,5-phenylene)tris(1H- tetrazole) (H3btt)

Wayne Ouellette, Kari Darling, Andrey Prosvirin, Kelly Whitenack, Kim R. Dunbar, Jon Zubieta

Research output: Contribution to journalArticle

35 Scopus citations

Abstract

The hydrothermal chemistry of a variety of M(ii)SO4 salts with the tetrazole (Ht) ligands 5,5′-(1,4-phenylene)bis(1H-tetrazole) (H 2bdt), 5′,5′′-(1,1′-biphenyl)4,4′- diylbis(1H-tetrazole) (H2dbdt) and 5,5′,5′′-(1,3,5- phenylene)tris(1H-tetrazole) (H3btt) was investigated. In the case of Co(ii), three phases were isolated, two of which incorporated sulfate: [Co 5F2(dbdt)4(H2O)6] ·2H2O (1·2H2O), [Co4(OH) 2(SO4)(bdt)2(H2O)4] (2) and [Co3(OH)(SO4)(btt)(H2O)4] ·3H2O (3·3H2O). The structures are three-dimensional and consist of cluster-based secondary building units: the pentanuclear {Co5F2(tetrazolate)8(H 2O)6}, the tetranuclear {Co4(OH) 2(SO4)2(tetrazolate)6} 4-, and the trinuclear {Co33-OH)(SO 4)2 (tetrazolate)3}2- for 1, 2, and 3, respectively. The Ni(ii) analogue [Ni2(H0.67bdt) 3]·10.5H2O (4·10.5H2O) is isomorphous with a fourth cobalt phase, the previously reported [Co 2(H0.67bat)3]·20H2O and exhibits a {M(tetrazolate)3/2} chain as the fundamental building block. The dense three-dimensional structure of [Zn(bdt)] (5) consists of {ZnN4}tetrahedra linked through bdt ligands bonding through N1,N3 donors at either tetrazolate terminus. In contrast to the hydrothermal synthesis of 1-5, the Cd(ii) material (Me2NH 2)3[Cd12Cl3(btt)8(DMF) 12]·xDMF·yMeOH (DMF = dimethylformamide; x = ca. 12, y = ca. 5) was prepared in DMF/methanol. The structure is constructed from the linking of {Cd4Cl(tetrazolate)8(DMF)4} 1- secondary building units to produce an open-framework material exhibiting 66.5% void volume. The magnetic properties of the Co(ii) series are reflective of the structural building units.

Original languageEnglish (US)
Pages (from-to)12288-12300
Number of pages13
JournalDalton Transactions
Volume40
Issue number45
DOIs
StatePublished - Dec 7 2011

ASJC Scopus subject areas

  • Inorganic Chemistry

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