TY - JOUR
T1 - Solid-state coordination chemistry of the Cu/triazolate/X system (X = F-, Cl-, Br-, I-, OH-, and SO42-)
AU - Ouellette, Wayne
AU - Prosvirin, Andrey V.
AU - Chieffo, Vincent
AU - Dunbar, Kim R.
AU - Hudson, Bruce
AU - Zubieta, Jon
PY - 2006/11/13
Y1 - 2006/11/13
N2 - Hydrothermal reactions of 1,2,4-triazole with the appropriate copper salt have provided eight structurally unique members of the Cu/triazolate/X system, with X = F-, Cl-, Br, l-, OH-, and SO42-. The anionic components X of [Cu3(trz) 4(H2O)3]F2 (1) and [Cu 6(trz)4Br]Cu4Br4(OH) (4) do not participate in the framework connectivity, acting as isolated charge-compensating counterions. In contrast, the anionic subunits X of [Cu IICuI(trz)Cl2] (2), [Cu6(trz) 4Br2] (3), [CuIICuI(trz)Br 2] (5), [Cu3(trz)I2] (6), [Cu6 IICu2I(trz)6(SO4) 3(OH)2(H2O)] (8), and [Cu4(trz) 3]OH·7.5H2O (9·7.5H2O) are intimately involved in the three-dimensional connectivities. The structure of [CuIICuI(trz)2][Cu3 Il4] (7) is constructed from two independent substructures: a three-dimensional cationic {Cu2(trz) 2}nn+ component and {Cu3l 4}nn- chains. Curiously, four of the structures are mixed-valence CuI/CuII materials: 2, 5, 7, and 8. The only CuII species is 1, while 3, 4, 6, and 9·7.5H2O exhibit exclusively CuI sites. The magnetic properties of the Cu II species 1 and of the mixed-valence materials 5, 7, 8, and the previously reported [Cu3(trz)3OH][Cu2Br 4] have been studied. The temperature-dependent magnetic susceptibility of 1 conforms to a simple isotropic model above 13 K, while below this temperature, there is weak ferromagnetic ordering due to spin canting of the antiferromagnetically coupled trimer units. Compounds 5 and 7 exhibit magnetic properties consistent with a one-dimensional chain model. The magnetic data for 8 were fit over the temperature range 2-300 K using the molecular field approximation with J = 204 cm-1, g = 2.25, and zJ′ = -38 cm-1. The magnetic properties of [Cu3(trz) 3OH][Cu2Br4] are similar to those of 8, as anticipated from the presence of similar triangular {Cu3(trz) 3(μ3-OH)}2+ building blocks. The Cu I species 3, 4, 6, and 9 as well as the previously reported [Cu 5(trz)3Cl2] exhibit luminescence thermochromism. The spectra are characterized by broad emissions, long lifetimes, and significant Stokes' shifts, characteristic of phosphorescence.
AB - Hydrothermal reactions of 1,2,4-triazole with the appropriate copper salt have provided eight structurally unique members of the Cu/triazolate/X system, with X = F-, Cl-, Br, l-, OH-, and SO42-. The anionic components X of [Cu3(trz) 4(H2O)3]F2 (1) and [Cu 6(trz)4Br]Cu4Br4(OH) (4) do not participate in the framework connectivity, acting as isolated charge-compensating counterions. In contrast, the anionic subunits X of [Cu IICuI(trz)Cl2] (2), [Cu6(trz) 4Br2] (3), [CuIICuI(trz)Br 2] (5), [Cu3(trz)I2] (6), [Cu6 IICu2I(trz)6(SO4) 3(OH)2(H2O)] (8), and [Cu4(trz) 3]OH·7.5H2O (9·7.5H2O) are intimately involved in the three-dimensional connectivities. The structure of [CuIICuI(trz)2][Cu3 Il4] (7) is constructed from two independent substructures: a three-dimensional cationic {Cu2(trz) 2}nn+ component and {Cu3l 4}nn- chains. Curiously, four of the structures are mixed-valence CuI/CuII materials: 2, 5, 7, and 8. The only CuII species is 1, while 3, 4, 6, and 9·7.5H2O exhibit exclusively CuI sites. The magnetic properties of the Cu II species 1 and of the mixed-valence materials 5, 7, 8, and the previously reported [Cu3(trz)3OH][Cu2Br 4] have been studied. The temperature-dependent magnetic susceptibility of 1 conforms to a simple isotropic model above 13 K, while below this temperature, there is weak ferromagnetic ordering due to spin canting of the antiferromagnetically coupled trimer units. Compounds 5 and 7 exhibit magnetic properties consistent with a one-dimensional chain model. The magnetic data for 8 were fit over the temperature range 2-300 K using the molecular field approximation with J = 204 cm-1, g = 2.25, and zJ′ = -38 cm-1. The magnetic properties of [Cu3(trz) 3OH][Cu2Br4] are similar to those of 8, as anticipated from the presence of similar triangular {Cu3(trz) 3(μ3-OH)}2+ building blocks. The Cu I species 3, 4, 6, and 9 as well as the previously reported [Cu 5(trz)3Cl2] exhibit luminescence thermochromism. The spectra are characterized by broad emissions, long lifetimes, and significant Stokes' shifts, characteristic of phosphorescence.
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U2 - 10.1021/ic061102e
DO - 10.1021/ic061102e
M3 - Article
C2 - 17083234
AN - SCOPUS:33751284075
SN - 0020-1669
VL - 45
SP - 9346
EP - 9366
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 23
ER -