Mixed ground-state in the trinuclear complex: [Mn3O(O 2CCCl3)6(H2O)3]

Hui Lien Tsai, Tyn Yih Jwo, Chen I. Yang, Ching Shuei Wur, Gene Hsiang Lee, Yu Wang

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4 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)1139-1146
Number of pages8
JournalJournal of the Chinese Chemical Society
Volume50
Issue number6
DOIs
Publication statusPublished - 2003

All Science Journal Classification (ASJC) codes

  • General Chemistry

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