Antisymmetric Exchange in Triangular Tricopper(II) Complexes: Correlation among Structural, Magnetic, and Electron Paramagnetic Resonance Parameters
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- 作者：Sacramento Ferrer ; Francesc Lloret ; Emilio Pardo ; Juan Modesto Clemente-Juan ; Malva Liu-Gonz谩lez ; Santiago Garc铆a-Granda
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：January 16, 2012
- 年：2012
- 卷：51
- 期：2
- 页码：985-1001
- 全文大小：813K
- 年卷期：v.51,no.2(January 16, 2012)
- ISSN：1520-510X
文摘
Two new trinuclear copper(II) complexes, [Cu3(渭3-OH)(daat)(Hdat)2(ClO4)2(H2O)3](ClO4)2路2H2O (1) and [Cu3(渭3-OH)(aaat)3(H2O)3](ClO4)2路3H2O (2) (daat = 3,5-diacetylamino-1,2,4-triazolate, Hdat = 3,5-diamino-1,2,4-triazole, and aaat = 3-acetylamino-5-amino-1,2,4-triazolate), have been prepared from 1,2,4-triazole derivatives and structurally characterized by X-ray crystallography. The structures of 1 and 2 consist of cationic trinuclear copper(II) complexes with a Cu3OH core held by three N,N-triazole bridges between each pair of copper(II) atoms. The copper atoms are five-coordinate with distorted square-pyramidal geometries. The magnetic properties of 1 and 2 and those of five other related 1,2,4-triazolato tricopper(II) complexes with the same triangular structure (3鈥?) (whose crystal structures were already reported) have been investigated in the temperature range of 1.9鈥?00 K. The formulas of 3鈥? are [Cu3(渭3-OH)(aaat)3(H2O)3](NO3)2路H2O (3), {[Cu3(渭3-OH)(aat)3(渭3-SO4)]路6H2O}n (4), and [Cu3(渭3-OH)(aat)3A(H2O)2]A路xH2O [A = NO3鈥?/sup> (5), CF3SO3鈥?/sup> (6), or ClO4鈥?/sup> (7); x = 0 or 2] (aat =3-acetylamino-1,2,4-triazolate). The magnetic and electron paramagnetic resonance (EPR) data have been analyzed by using the following isotropic and antisymmetric exchange Hamiltonian: H = 鈥?i>J[S1S2 + S2S3] 鈥?j[S1S3] + G[S1 脳 S2 + S2 脳 S3 + S1 脳 S3]. 1鈥?b>7 exhibit strong antiferromagnetic coupling (values for both 鈥?i>J and 鈥?i>j in the range of 210鈥?42 cm鈥?) and antisymmetric exchange (G varying from to 27 to 36 cm鈥?). At low temperatures, their EPR spectra display high-field (g < 2.0) signals indicating that the triangles present symmetry lower than equilateral and that the antisymmetric exchange is operative. A magneto-structural study showing a lineal correlation between the Cu鈥揙鈥揅u angle of the Cu3OH core and the isotropic exchange parameters (J and j) has been conducted. Moreover, a model based on Moriya鈥檚 theory that allows the prediction of the occurrence of antisymmetric exchange in the tricopper(II) triangles, via analysis of the overlap between the ground and excited states of the local Cu(II) ions, has been proposed. In addition, analytical expressions for evaluating both the isotropic and antisymmetric exchange parameters from the experimental magnetic susceptibility data of triangular complexes with local spins (S) of 1/2, 3/2, or 5/2 have been purposely derived. Finally, the magnetic and EPR results of this work are discussed and compared with those of other tricopper(II) triangles reported in the literature.