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2-氨基异丁酸在 Co(II)和 Co(II)/Ln(III)化学中的应用：同金属和杂金属簇合物。

2-Aminoisobutyric acid in Co(II) and Co(II)/Ln(III) chemistry: homometallic and heterometallic clusters.

机构信息

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

出版信息

Inorg Chem. 2012 Jan 16;51(2):1170-9. doi: 10.1021/ic2024007. Epub 2011 Dec 22.

DOI:10.1021/ic2024007
PMID:22220944
Abstract

The synthesis and magnetic properties of 13 new homo- and heterometallic Co(II) complexes containing the artificial amino acid 2-amino-isobutyric acid, aibH, are reported: Co(II)(4)(aib)(3)(aibH)(3)(NO(3))(4)·2.8CH(3)OH·0.2H(2)O (1·2.8CH(3)OH·0.2H(2)O), {Na(2)[Co(II)(2)(aib)(2)(N(3))(4)(CH(3)OH)(4)]}(n) (2), [Co(II)(6)La(III)(aib)(6)(OH)(3)(NO(3))(2)(H(2)O)(4)(CH(3)CN)(2)]·0.5[La(NO(3))(6)]·0.75(ClO(4))·1.75(NO(3))·3.2CH(3)CN·5.9H(2)O (3·3.2CH(3)CN·5.9H(2)O), [Co(II)(6)Pr(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Pr(NO(3))(5)]·0.41[Pr(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.59[Co(NO(3))(3)(H(2)O)]·0.2(ClO(4))·0.25H(2)O (4·0.25H(2)O), [Co(II)(6)Nd(III)(aib)(6)(OH)(3)(NO(3))(2.8)(CH(3)OH)(4.7)(H(2)O)(1.5)]·2.7(ClO(4))·0.5(NO(3))·2.26CH(3)OH·0.24H(2)O (5·2.26CH(3)OH·0.24H(2)O), [Co(II)(6)Sm(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Sm(NO(3))(5)]·0.44[Sm(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.56[Co(NO(3))(3)(H(2)O)]·0.22(ClO(4))·0.3H(2)O (6·0.3H(2)O), Co(II)(6)Eu(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)OH)(4.87)(H(2)O)(1.13)(2.5)(NO(3))(0.5)·2.43CH(3)OH·0.92H(2)O (7·2.43CH(3)OH·0.92H(2)O), [Co(II)(6)Gd(III)(aib)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.9)(H(2)O)(1.2)]·2.6(ClO(4))·0.5(NO(3))·2.58CH(3)OH·0.47H(2)O (8·2.58CH(3)OH·0.47H(2)O), [Co(II)(6)Tb(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Tb(NO(3))(5)]·0.034[Tb(NO(3))(3)(ClO(4))(0.5)(H(2)O)(0.5)]·0.656[Co(NO(3))(3)(H(2)O)]·0.343(ClO(4))·0.3H(2)O (9·0.3H(2)O), Co(II)(6)Dy(III)(aib)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.92)(H(2)O)(1.18)(2.6)(NO(3))(0.5)·2.5CH(3)OH·0.5H(2)O (10·2.5CH(3)OH·0.5H(2)O), [Co(II)(6)Ho(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·0.27[Ho(NO(3))(3)(ClO(4))(0.35)(H(2)O)(0.15)]·0.656[Co(NO(3))(3)(H(2)O)]·0.171(ClO(4)) (11), Co(II)(6)Er(III)(aib)(6)(OH)(4)(NO(3))(2)(CH(3)CN)(2.5)(H(2)O)(3.5)(3)·CH(3)CN·0.75H(2)O (12·CH(3)CN·0.75H(2)O), and [Co(II)(6)Tm(III)(aib)(6)(OH)(3)(NO(3))(3)(H(2)O)(6)]·1.48(ClO(4))·1.52(NO(3))·3H(2)O (13·3H(2)O). Complex 1 describes a distorted tetrahedral metallic cluster, while complex 2 can be considered to be a 2-D coordination polymer. Complexes 3-13 can all be regarded as metallo-cryptand encapsulated lanthanides in which the central lanthanide ion is captivated within a [Co(II)(6)] trigonal prism. dc and ac magnetic susceptibility studies have been carried out in the 2-300 K range for complexes 1, 3, 5, 7, 8, 10, 12, and 13, revealing the possibility of single molecule magnetism behavior for complex 10.

摘要

合成和磁性的 13 个新的同和异金属 Co(II) 配合物含有人工氨基酸 2-氨基异丁酸，AIBH，报道：Co(II)(4)(AIB)(3)(AIBH)(3)(NO(3))(4)·2.8CH(3)OH·0.2H(2)O (1·2.8CH(3)OH·0.2H(2)O)，{Na(2)[Co(II)(2)(AIB)(2)(N(3))(4)(CH(3)OH)(4)]}(n) (2)，[Co(II)(6)La(III)(AIB)(6)(OH)(3)(NO(3))(2)(H(2)O)(4)(CH(3)CN)(2)]·0.5[La(NO(3))(6)]·0.75(ClO(4))·1.75(NO(3))·3.2CH(3)CN·5.9H(2)O (3·3.2CH(3)CN·5.9H(2)O)，[Co(II)(6)Pr(III)(AIB)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Pr(NO(3))(5)]·0.41[Pr(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.59[Co(NO(3))(3)(H(2)O)]·0.2(ClO(4))·0.25H(2)O (4·0.25H(2)O)，[Co(II)(6)Nd(III)(AIB)(6)(OH)(3)(NO(3))(2.8)(CH(3)OH)(4.7)(H(2)O)(1.5)]·2.7(ClO(4))·0.5(NO(3))·2.26CH(3)OH·0.24H(2)O (5·2.26CH(3)OH·0.24H(2)O)，[Co(II)(6)Sm(III)(AIB)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Sm(NO(3))(5)]·0.44[Sm(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.56[Co(NO(3))(3)(H(2)O)]·0.22(ClO(4))·0.3H(2)O (6·0.3H(2)O)，Co(II)(6)Eu(III)(AIB)(6)(OH)(3)(NO(3))(3)(CH(3)OH)(4.87)(H(2)O)(1.13)(2.5)(NO(3))(0.5)·2.43CH(3)OH·0.92H(2)O (7·2.43CH(3)OH·0.92H(2)O)，[Co(II)(6)Gd(III)(AIB)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.9)(H(2)O)(1.2)]·2.6(ClO(4))·0.5(NO(3))·2.58CH(3)OH·0.47H(2)O (8·2.58CH(3)OH·0.47H(2)O)，[Co(II)(6)Tb(III)(AIB)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Tb(NO(3))(5)]·0.034[Tb(NO(3))(3)(ClO(4))(0.5)(H(2)O)(0.5)]·0.656[Co(NO(3))(3)(H(2)O)]·0.343(ClO(4))·0.3H(2)O (9·0.3H(2)O)，Co(II)(6)Dy(III)(AIB)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.92)(H(2)O)(1.18)(2.6)(NO(3))(0.5)·2.5CH(3)OH·0.5H(2)O (10·2.5CH(3)OH·0.5H(2)O)，[Co(II)(6)Ho(III)(AIB)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·0.27[Ho(NO(3))(3)(ClO(4))(0.35)(H(2)O)(0.15)]·0.656[Co(NO(3))(3)(H(2)O)]·0.171(ClO(4)) (11)，Co(II)(6)Er(III)(AIB)(6)(OH)(4)(NO(3))(2)(CH(3)CN)(2.5)(H(2)O)(3.5)(3)·CH(3)CN·0.75H(2)O (12·CH(3)CN·0.75H(2)O)，和[Co(II)(6)Tm(III)(AIB)(6)(OH)(3)(NO(3))(3)(H(2)O)(6)]·1.48(ClO(4))·1.52(NO(3))·3H(2)O (13·3H(2)O)。复合物 1 描述了一个扭曲的四面体金属簇，而复合物 2 可以被认为是一个二维配位聚合物。复合物 3-13 都可以被视为金属笼包裹镧系元素，其中中心镧系元素离子被囚禁在一个[Co(II)(6)]三角棱柱中。在 2-300 K 范围内对复合物 1、3、5、7、8、10、12 和 13 进行了 dc 和 ac 磁化率研究，揭示了复合物 10 可能具有单分子磁体行为。

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