TY - JOUR
T1 - Mixed ground-state in the trinuclear complex
T2 - [Mn3O(O 2CCCl3)6(H2O)3]
AU - Tsai, Hui Lien
AU - Jwo, Tyn Yih
AU - Yang, Chen I.
AU - Wur, Ching Shuei
AU - Lee, Gene Hsiang
AU - Wang, Yu
PY - 2003
Y1 - 2003
N2 - The reaction of [Mn12O12(OAc)16(H 2O)4]-4H2O·2HOAc with Cl 3CCO2H in dichloromethane leads to formation of mixed-valence trinuclear oxo-centered [Mn3O(O2CCCl 3)6(H2O)3]·2H2O (1). Complex 1 crystallizes in two forms; the monoclinic and hexagonal systems. [Mn3O(O2CCCl3)6(H2O) 3]·3H2O (1a) crystallizes in hexagonal, space group P63/m (295 K) with a = 10.0741(1) Å, c = 22.8668(4) Å and z = 2. [Mn3O(O2CCCl3)6(H 2O)3]·0.5C6H14 (1b) crystallizes in monoclinic, space group P21/n (150 K) with a = 11.8258(2) Å, b = 41.9370(5) Å, c = 25.9619(4) Å, β = 95.297(1)°, and z = 12. Complex 1 possesses an oxo-centered Mn3O unit with peripheral ligands provided by bridging trichloroacetate and terminal H2O groups. Each manganese ion is distorted octahedral, and consideration of overall charge of the trinuclear unit necessitates a mixed-valence MNIIMnIII2 description. Magnetization measurement at 2.0 K up to 70 kG indicates the mixed ground state S = 3/2 and S = 1/2 for complex 1. X-band EPR spectra measured at 4.0-100.0 K on polycrystalline sample of complex 1. There is a transition centered at g = 4, which decreases in intensity with increasing temperature. Also, there is a transition centered at g = 2, which does not disappear with increasing temperature.
AB - The reaction of [Mn12O12(OAc)16(H 2O)4]-4H2O·2HOAc with Cl 3CCO2H in dichloromethane leads to formation of mixed-valence trinuclear oxo-centered [Mn3O(O2CCCl 3)6(H2O)3]·2H2O (1). Complex 1 crystallizes in two forms; the monoclinic and hexagonal systems. [Mn3O(O2CCCl3)6(H2O) 3]·3H2O (1a) crystallizes in hexagonal, space group P63/m (295 K) with a = 10.0741(1) Å, c = 22.8668(4) Å and z = 2. [Mn3O(O2CCCl3)6(H 2O)3]·0.5C6H14 (1b) crystallizes in monoclinic, space group P21/n (150 K) with a = 11.8258(2) Å, b = 41.9370(5) Å, c = 25.9619(4) Å, β = 95.297(1)°, and z = 12. Complex 1 possesses an oxo-centered Mn3O unit with peripheral ligands provided by bridging trichloroacetate and terminal H2O groups. Each manganese ion is distorted octahedral, and consideration of overall charge of the trinuclear unit necessitates a mixed-valence MNIIMnIII2 description. Magnetization measurement at 2.0 K up to 70 kG indicates the mixed ground state S = 3/2 and S = 1/2 for complex 1. X-band EPR spectra measured at 4.0-100.0 K on polycrystalline sample of complex 1. There is a transition centered at g = 4, which decreases in intensity with increasing temperature. Also, there is a transition centered at g = 2, which does not disappear with increasing temperature.
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U2 - 10.1002/jccs.200300161
DO - 10.1002/jccs.200300161
M3 - Article
AN - SCOPUS:33144464658
SN - 0009-4536
VL - 50
SP - 1139
EP - 1146
JO - Journal of the Chinese Chemical Society
JF - Journal of the Chinese Chemical Society
IS - 6
ER -