TY - JOUR
T1 - Hydrothermal synthesis, structural chemistry, and magnetic properties of materials of the MII/triazolate/anion family, where MII = Mn, Fe, and Ni
AU - Ouellette, Wayne
AU - Prosvirin, Andrey V.
AU - Valeich, Jamie
AU - Dunbar, Kim R.
AU - Zubieta, Jon
PY - 2007/10/29
Y1 - 2007/10/29
N2 - Hydrothermal chemistry has been exploited in the preparation of a series of manganese(II), iron(II), and nickel(II) triazolate frameworks, [Mn 7(trz)8(CH3CO2)4(OH) 2]·2.5H2O (1·2.5H2O), [Mn 5(Htrz)2(SO4)4(OH)2] (2), [Fe5(Htrz)2(SO4)4-(OH)2] (3), [Fe3(Htrz)3(HSO4)(SO4) 2(OH)]·H2O (4·H2O), [Ni 3(trz)3(OH)3(H2O) 4]·5H2O (5·5H2O), and [Ni 3(trz)5(OH)]·2.5H2O (6·2.5H 2O). The materials all exhibit three-dimensional structures, reflecting the tendency of triazole/triazolate ligands to bridge multiple metal sites. A prominent characteristic of the structures is the presence of embedded metal clusters as building blocks: heptanuclear MnII units in 1, pentanuclear MII sites in 2 and 3, and trinuclear MII clusters in 4 and 5. The presence of the pentanuclear and trinuclear clusters of magnetic metal cations in 2-5 is reflected in the unusual magnetic characteristics of these materials, all of which exhibit spin frustration. The compound 5·5H2O reversibly desorbs/sorbs solvent. However, the dehydrated phase does not adsorb methanol, N2, O2, or H2, presumably as a consequence of the highly polar void volume and the narrow channels connecting the larger cavities of the void structure.
AB - Hydrothermal chemistry has been exploited in the preparation of a series of manganese(II), iron(II), and nickel(II) triazolate frameworks, [Mn 7(trz)8(CH3CO2)4(OH) 2]·2.5H2O (1·2.5H2O), [Mn 5(Htrz)2(SO4)4(OH)2] (2), [Fe5(Htrz)2(SO4)4-(OH)2] (3), [Fe3(Htrz)3(HSO4)(SO4) 2(OH)]·H2O (4·H2O), [Ni 3(trz)3(OH)3(H2O) 4]·5H2O (5·5H2O), and [Ni 3(trz)5(OH)]·2.5H2O (6·2.5H 2O). The materials all exhibit three-dimensional structures, reflecting the tendency of triazole/triazolate ligands to bridge multiple metal sites. A prominent characteristic of the structures is the presence of embedded metal clusters as building blocks: heptanuclear MnII units in 1, pentanuclear MII sites in 2 and 3, and trinuclear MII clusters in 4 and 5. The presence of the pentanuclear and trinuclear clusters of magnetic metal cations in 2-5 is reflected in the unusual magnetic characteristics of these materials, all of which exhibit spin frustration. The compound 5·5H2O reversibly desorbs/sorbs solvent. However, the dehydrated phase does not adsorb methanol, N2, O2, or H2, presumably as a consequence of the highly polar void volume and the narrow channels connecting the larger cavities of the void structure.
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U2 - 10.1021/ic700790h
DO - 10.1021/ic700790h
M3 - Article
C2 - 17910434
AN - SCOPUS:35848944127
SN - 0020-1669
VL - 46
SP - 9067
EP - 9082
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 22
ER -