Ferromagnetic Interactions in Heterobimetallic Chains Formed through the Secondary Coordination of Dithiolene Complexes

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• 作者：Olivier Jeannin ; Rodolphe Clé ; rac ; Thomas Cauchy ; Marc Fourmigué
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：November 17, 2008
• 年：2008
• 卷：47
• 期：22
• 页码：10656-10661
• 全文大小：275K
• 年卷期：v.47,no.22(November 17, 2008)
• ISSN：1520-510X

文摘

A novel paramagnetic (S = 1/2) copper dithiolene complex based on the tfadt ligand (tfadt: 3-trifluoromethyl-acrylonitrile-2,3-dithiolate) is prepared as its n-Bu₄N⁺ salt and crystallized with [Ni(cyclam)]²⁺ into infinite, one-dimensional chains through CN···Ni interactions, avoiding any direct (antiferromagnetic) overlap between the dithiolene complexes. An unprecedented ferromagnetic interaction within the heterobimetallic chains between the S = 1/2 [Cu(tfadt)₂]²⁻ and the S = 1 [Ni(cyclam)]²⁺ tectons is observed, despite the fact that the SOMOs of both [Cu(tfadt)₂]²⁻ (with d_x²−y² symmetry) and [Ni(cyclam)]²⁺ (with d_x²−y² and d_z² symmetry) have the same e_g symmetry. The experimental exchange interaction deduced from the fit of the magnetic susceptibility (J_exp/k_B = +5.0 K) was confirmed by theoretical calculations (J_calc/k_B = +7.3 K), and a rationale is given for the presence of an intrachain ferromagnetic interaction.