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镍(II)和镍(II)/镧系元素(III)化学中的人工氨基酸。

Artificial amino acids in nickel(II) and nickel(II)/lanthanide(III) chemistry.

机构信息

Department of Chemistry, The University of Crete, Voutes, 71003 Herakleion, Greece.

出版信息

Inorg Chem. 2011 Jun 6;50(11):5175-85. doi: 10.1021/ic2004744. Epub 2011 Apr 27.

Abstract

The synthesis and magnetic properties of five new homo- and heterometallic nickel(II) complexes containing artificial amino acids are reported: Ni(4)(aib)(3)(aibH)(3)(NO(3))(4)·3.05MeOH (1·3.05MeOH), Ni(6)La(aib)(12)(3)·5.5H(2)O (2·5.5H(2)O), Ni(6)Pr(aib)(12)(3)·5.5H(2)O (3·5.5H(2)O), [Ni(5)(OH)(2)(l-aba)(4)(OAc)(4)]·0.4EtOH·0.3H(2)O 6(4·0.4EtOH·0.3H(2)O), and [Ni(6)La(l-aba)(12)][La(2)(NO(3))(9)] (5; aibH = 2-aminoisobutyric acid; l-abaH = l-2-aminobutyric acid). Complexes 1 and 4 describe trigonal-pyramidal and square-based pyramidal metallic clusters, respectively, while complexes 2, 3, and 5 can be considered to be metallocryptand-encapsulated lanthanides. Complexes 4 and 5 are chiral and crystallize in the space groups I222 and P2(1)3, respectively. Direct-current magnetic susceptibility studies in the 2-300 K range for all complexes reveal the presence of dominant antiferromagnetic exchange interactions, leading to small or diamagnetic ground states.

摘要

报道了五个新的含有人工氨基酸的同核和异核镍(II)配合物的合成和磁性:Ni(4)(aib)(3)(aibH)(3)(NO(3))(4)·3.05MeOH(1·3.05MeOH)、Ni(6)La(aib)(12)(3)·5.5H(2)O(2·5.5H(2)O)、Ni(6)Pr(aib)(12)(3)·5.5H(2)O(3·5.5H(2)O)、[Ni(5)(OH)(2)(l-aba)(4)(OAc)(4)]·0.4EtOH·0.3H(2)O 6(4·0.4EtOH·0.3H(2)O)和[Ni(6)La(l-aba)(12)][La(2)(NO(3))(9)](5;aibH = 2-氨基异丁酸;l-abaH = l-2-氨基丁酸)。配合物 1 和 4 分别描述了三角双锥和四方锥金属簇,而配合物 2、3 和 5 可以被认为是金属笼包封的镧系元素。配合物 4 和 5 是手性的,分别在空间群 I222 和 P2(1)3 中结晶。所有配合物在 2-300 K 范围内的直流磁化率研究表明存在主导的反铁磁交换相互作用,导致较小或抗磁性的基态。

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