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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >A tetranuclear complex from the employment of pyridine-2,6-dimethanol in copper(II) nitrate chemistry: Synthetic, structural and magnetic studies
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A tetranuclear complex from the employment of pyridine-2,6-dimethanol in copper(II) nitrate chemistry: Synthetic, structural and magnetic studies

机译:吡啶-2-6-二甲醇在硝酸铜(II)化学中的应用所产生的四核配合物:合成,结构和磁性研究

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The use of pyridine-2,6-dimethanol (pdmH(2)) in copper(II) nitrate chemistry is reported. The reaction of Cu(NO3)(2)center dot 3H(2)O with one equivalent of pdmH(2) in MeCN affords the known mononuclear complex [Cu(pdmH(2))(2)](NO3)(2) (1) in high-yield. The reaction of I and NaOMe in an 1: 1 ratio, as well as the reaction between Cu(NO3)(2)center dot 3H(2)O, pdmH(2) and NaOMe in an 1:1:1 ratio, in MeOH gives the tetranuclear complex [Cu-4(NO3)(2)(pdmH)(4)(H2O)(MeOH)](NO3)(2) (2) in moderate yields. The cation of 2 possesses a slightly distorted tetrahedral Cu-4 topology with a [Cu-4(mu(2)-OR)(4)](4+) core. The pdmH(-) ions behave as eta(1):eta(1):eta(2):mu(2) ligands. Strong intramolecular hydrogen bonds and pi-pi stacking interactions provide thermodynamic stability on compound 2. Variable-temperature, solid-state dc magnetic studies were carried out on complex 2 in the 2.0-300 K range. The data indicate predominant antiferromagnetic exchange interactions and a resulting S = 0 ground state, which is expected for a solely, mu(2)-alkoxide-bridged system with obtuse Cu-O-Cu bond angles that magnetically behaves as a Cu-4 ring. A simplified 1 - J model was found to be adequate to describe the variable-temperature dc susceptibility data. The data were fitted to the appropriate equation derived from the Hamiltonian H = J(1)(S-1 center dot S-2 + S-2 center dot S-4 + S-3 center dot S-4 + S-1 center dot S-3), giving the parameters J(1) = -99.5 cm(-1) and g = 2.11(4). The combined work demonstrates the ligating flexibility of the pdmH(2) chelate and its usefulness in the synthesis of oligo- and polynuclear Cu-x(II) clusters with interesting structural and magnetic properties, without requiring the co-presence of carboxylate ligands.
机译:据报道在硝酸铜(II)化学中使用吡啶2,6-二甲醇(pdmH(2))。 Cu(NO3)(2)中心点3H(2)O与一当量的pdmH(2)在MeCN中的反应提供了已知的单核络合物[Cu(pdmH(2))(2)](NO3)(2) (1)高产。 I和NaOMe以1:1的比率进行反应,以及Cu(NO3)(2)中心点3H(2)O,pdmH(2)和NaOMe之间以1:1:1的比率进行反应MeOH以中等收率得到四核配合物[Cu-4(NO3)(2)(pdmH)(4)(H2O)(MeOH)](NO3)(2)(2)。 2的阳离子具有带[Cu-4(mu(2)-OR)(4)](4+)核的稍微扭曲的四面体Cu-4拓扑。 pdmH(-)离子表现为eta(1):eta(1):eta(2):mu(2)配体。强大的分子内氢键和pi-pi堆积相互作用为化合物2提供了热力学稳定性。在2.0-300 K范围内对复合物2进行了温度可变的固态dc磁研究。数据表明,主要的反铁磁交换相互作用和最终的S = 0基态,这对于具有钝化Cu-O-Cu键角且磁性表现为Cu-4环的纯mu(2)-醇盐桥联系统是期望的。发现简化的1-J模型足以描述可变温度dc磁化率数据。将数据拟合为从哈密顿量H = J(1)(S-1中心点S-2 + S-2中心点S-4 + S-3中心点S-4 + S-1中心)导出的适当方程式点S-3),参数为J(1)= -99.5 cm(-1),g = 2.11(4)。结合的工作证明了pdmH(2)螯合物的连接柔性及其在合成具有有趣的结构和磁性性质的寡核和多核Cu-x(II)簇中的有用性,而无需羧酸盐配体的共存。

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