| 酚氧桥联多核铜(Ⅱ)配合物的合成、结构和磁性 |
| Synthesis, Structure and Magnetic Properties of Phenoxo-Bridged Polynuclear Cu(Ⅱ) Complexes |
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| 摘要: 利用柔性酚胺类配体N,N'-二甲基-N,N'-(2-羟基-4,5-二甲基苄基)乙二胺(H2L)与Cu(Ⅱ)反应,合成了2个新的酚氧桥联多核Cu(Ⅱ)配合物[Cu3II(L)2(CH3OH)2](ClO4)2(1),[Cu3II(L)2(CuICl2)2](2)。配合物1~2中,3个Cu2+之间通过2个酚氧桥连接,形成线性三核结构。两边的铜离子分别被配体L2-上的N2O2螯合配位,轴向与甲醇分子的氧(配合物1)或[CuCl2]-的氯(配合物2)配位,形成四方锥配位构型。中间铜离子与两侧L2-上的4个酚氧原子以平面四边形配位。CuII-O-CuII键角为100.14°~101.79°。对配合物1~2进行变温磁化率测量表明,铜离子之间通过酚氧桥存在强的反铁磁耦合,磁耦合常数J分别为-277(9)cm-1(配合物1)和-299(3)cm-1(配合物2)(基于自旋哈密顿算符Ĥ=-2J(Ŝ1·Ŝ2+Ŝ2·Ŝ3)。J值与酚氧桥桥联键角有一定相关性,即Cu-O-Cu桥联键角越大,反铁磁耦合越强。 |
| 关键词: 柔性配体 铜 多核配合物 磁性 混合价 |
| 基金项目: 国家重点基础研究发展计划(No.2013CB933403)和国家自然科学基金(No.91222104,21771103,20121318518)资助项目。 |
| Abstract: Two polynuclear copper complexes containing the flexible ligand N, N'-dimethyl-N, N'-(2-hydroxy-4, 5-dimethylbenzyl)ethylenediamine (H2L) have been prepared and characterized structurally and magnetically. The complexes have the formula [Cu3II(L)2(CH3OH)2](ClO4)2(1) and [Cu3II(L)2(CuICl2)2](2). X-ray single-crystal structure analyses show that both complexes contain linear CuII-CuII-CuII cores where adjacent Cu(Ⅱ) ions are doubly bridged by phenolate groups of L2-. The coordination sphere of the terminal Cu(Ⅱ) ions is square pyramidal with the methanol oxygen (complex 1) or the chloride ion of [CuCl2]- (complex 2) situated at the apical position, whereas the central Cu(Ⅱ) has a square coordination environment. The CuII-O-CuII bridging bond angles are in the range of 100.14°~101.79°. Magnetic studies show that both complexes exhibit strong antiferromagnetic interaction with the spin exchange coupling constants (J) of -277(9) cm-1 (1) and -299(3) cm-1 (2) (Ĥ=-2J(Ŝ1·Ŝ2+Ŝ2·Ŝ3). The antiferromagnetic interactions have been found to be mainly related to the CuII-O-CuII bond angles. Larger Cu-O-Cu bond angles correspond to stronger antiferromagnetic interaction (more negative J values). |
| Keywords: flexible ligand copper polynuclear magnetism mixed-valent |
| 投稿时间：2014-05-07 修订日期：2015-06-02 |
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| 谢齐威,崔爱莉,寇会忠.酚氧桥联多核铜(Ⅱ)配合物的合成、结构和磁性[J].无机化学学报,2015,31(9):1798-1804. |
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