Nitrophenolate as a building block for lanthanide chains, layers, and clusters
Nitrophenolate as a building block for lanthanide chains, layers, and clusters
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DOI：
10.1021/ja0396044
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发表时间：
2004-04-28
影响因子：
15
通讯作者：
Roesky, PW
中科院分区：
文献类型：
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作者：
B端rgstein, MR;Gamer, MT;Roesky, PW
在不同的反应条件下，邻硝基苯酚钾（1）与不同的三氯化稀土反应。通过使用较小的镧系元素并在严格排除空气的条件下工作，得到了组成为[（THF）（4）{K（o-O_2N-C_6 H_4-O）（4）Ln}（4）]（n）（Ln = Y（2a），Er（2b），Lu（2c））的无限长链。使用相同的条件，但在空气中进行结晶，分离组成为H-18[Ln（14）（mu-eta（2）-o-O2 N-C6 H4-O）（8）（eta（2）-o-O2 N-C6 H4-O）（16）（mu（4）-O）（2）（mu（3）-O）（16）]（Ln = Dy（3a），Er（3b），Tm（3c），Yb（3d））的十四核簇。使用较大的中心金属如钐、铕和铽，并在严格排除空气的条件下工作，得到了组成为[[K-2（o-O_2N-C_6 H_4-O）（5）Tb]（n）]（4）和[[K-2（o-O_2N-C_6 H_4 O）（5）Ln）]（n）]（Ln = Sm（5a），Eu（5 b））的无限层。在4中，层具有比化合物5中的层更紧密的堆积。紧密堆积是镧系金属和钾原子的配位数增加的结果。相比之下，5的更开放的结构导致穿过层的矩形通道。所有的化合物包括1已经通过单晶X-射线衍射进行了研究。
Potassium o-nitrophenolate (1) was reacted with various lanthanide trichlorides under different reaction conditions. By using the smaller lanthanides and working under rigorous exclusion of air, infinite chains of composition [(THF)(4){K(o-O2N-C6H4-O)(4)Ln}(4)](n) (Ln = Y (2a), Er (2b), Lu (2c)) were obtained. Using the same conditions but performing the crystallization under air, tetradecanuclear clusters of composition H-18[Ln(14)(mu-eta(2)-o-O2N-C6H4-O)(8)(eta(2)-o-O2N-C6H4-O)(16)(mu(4)-O)(2)(mu(3)-O)(16)] (Ln = Dy (3a), Er (3b), Tm (3c), Yb (3d)) were isolated. Using larger center metals such as samarium, europium, and terbium and working under rigorous exclusion of air, infinite layers of composition [[K-2(o-O2N-C6H4-O)(5)Tb](n)] (4) and [[K-2(o-O2N-C6H4O)(5)Ln)](n)] (Ln = Sm (5a), Eu (5b)) were obtained. In 4 the layers have a closer packing than those in compound 5. The closer packing is a result of the increased coordination number of the lanthanide metal and the potassium atoms. In contrast, the more open structures of 5 results in channels which are rectangular through the layers. All compounds reported including 1 have been investigated by single-crystal X-ray diffraction.