TY - JOUR
T1 - 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)
AU - Ouellette, Wayne
AU - Darling, Kari
AU - Prosvirin, Andrey
AU - Whitenack, Kelly
AU - Dunbar, Kim R.
AU - Zubieta, Jon
PY - 2011/12/7
Y1 - 2011/12/7
N2 - 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 {Co3(μ3-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.
AB - 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 {Co3(μ3-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.
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U2 - 10.1039/c1dt11590a
DO - 10.1039/c1dt11590a
M3 - Article
C2 - 21971918
AN - SCOPUS:81255138769
SN - 1477-9226
VL - 40
SP - 12288
EP - 12300
JO - Dalton Transactions
JF - Dalton Transactions
IS - 45
ER -