Halide-templated assembly of polynuclear lanthanide-hydroxo complexes.
Halide-templated assembly of polynuclear lanthanide-hydroxo complexes.
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DOI：
10.1021/ic010859x
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发表时间：
2002-01
影响因子：
4.6
通讯作者：
Ruiyao Wang;H. Selby;Hui Liu;M. Carducci;T. Jin;Zhiping Zheng;J. Anthis;R. Staples
中科院分区：
文献类型：
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作者：
Ruiyao Wang;H. Selby;Hui Liu;M. Carducci;T. Jin;Zhiping Zheng;J. Anthis;R. Staples
通过在添加Cl⁻或Br⁻的情况下，用L - 酪氨酸控制相应镧系高氯酸盐的水解，制备了一系列具有通式[Ln₁₅(μ₃ - OH)₂₀(μ₅ - X)]²⁴⁺的十五核镧系 - 羟基配合物（1，Ln = Eu，X = Cl⁻；2，Ln = Nd，X = Cl⁻；3，Ln = Gd，X = Cl⁻；4，Ln = Pr，X = Br⁻；5，Ln = Eu，X = Br⁻）。阳离子簇核由五个以卤离子为模板的顶点共享的立方烷状[Ln₄(μ₃ - OH)₄]⁸⁺单元组成。在以I⁻为模板的情况下，分离得到的是十二核配合物。核心组分[Ln₁₂(μ₃ - OH)₁₆(I)₂]¹⁸⁺（6，Ln = Dy；7，Ln = Er）由四个顶点共享的立方烷状[Ln₄(μ₃ - OH)₄]⁸⁺单元组成，并且作为一种方形环状结构存在，在方形平面的每一侧有一个I⁻。一个涉及Er(NO₃)₃、L - 酪氨酸和NaOH的类似水解反应得到了已知的六核配合物[Er₆(μ₆ - O)(μ₃ - OH)₈(NO₃)₆(H₂O)₁₂](NO₃)₂，其核心组分是一个带有间隙μ₆ - 氧代基团的面心立方八面体[Er₆(μ₆ - O)(μ₃ - OH)₈]⁸⁺簇（Wang, R.；Carducci, M. D.；Zheng, Z.《无机化学》2000年，39卷，1836 - 1837页）。卤离子包封的多立方烷配合物（1 - 7）的高效自组装以及无法生成类似的含硝酸根配合物，证明了卤离子所起的优越模板作用。当在有竞争的Cl⁻存在的情况下进行酪氨酸辅助的Gd(NO₃)₃水解时，分离得到阳离子十五核配合物3作为唯一产物，这进一步证实了卤离子的模板效应。使用埃文斯方法在室温下测量的配合物1 - 7的磁矩与根据范弗莱克方程计算的值非常吻合，假设镧系离子之间没有磁相互作用。
A series of pentadecanuclear lanthanide-hydroxo complexes possessing a common core of the formula [Ln(15)(mu(3)-OH)(20)(mu(5)-X)](24+)(1, Ln = Eu, X = Cl(-); 2, Ln = Nd, X = Cl(-); 3, Ln = Gd, X = Cl(-); 4, Ln = Pr, X = Br(-); 5, Ln = Eu, X = Br(-)) were prepared by L-tyrosine-controlled hydrolysis of corresponding lanthanide perchlorates in the presence of added Cl(-) or Br(-). The cationic cluster core comprises five vertex-sharing cubane-like [Ln(4)(mu(3)-OH)(4)](8+) units centered on the halide template. In the case of templating I(-), dodecanuclear complexes were isolated instead. The core component, [Ln(12)(mu(3)-OH)(16)(I)(2)](18+) (6, Ln = Dy; 7, Ln = Er), consists of four vertex-sharing cubane-like [Ln(4)(mu(3)-OH)(4)](8+) units and exists as a square-shaped cyclic structure with one I(-) located on each side of the square plane. An analogous hydrolytic reaction involving Er(NO(3))(3), L-tyrosine, and NaOH affords the known hexanuclear complex [Er(6)(mu(6)-O)(mu(3)-OH)(8)(NO(3))(6)(H(2)O)(12)](NO(3))(2) whose core component is a face-capped octahedral [Er(6)(mu(6)-O)(mu(3)-OH)(8)](8+) cluster with an interstitial mu(6)-oxo group (Wang, R.; Carducci, M. D.; Zheng, Z. Inorg. Chem. 2000, 39, 1836-1837.). The efficient self-assembly of halide-encapsulating multicubane complexes (1-7) and the inability to produce an analogous nitrate-containing complex demonstrate the superior templating roles played by the halide ion(s). Further credence for the halide template effects was provided by the isolation of the cationic pentadecanuclear complex 3 as the sole product when tyrosine-supported hydrolysis of Gd(NO(3))(3) was carried out in the presence of competitive Cl(-). Magnetic moments of complexes 1-7 measured at room temperature by using Evans' method are in excellent agreement with those calculated by the Van Vleck equation, assuming magnetically noninteractive lanthanide ions.