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首页> 外文期刊>Chemistry: A European journal >Synthesis of New Self-assembled Pd~(II) and Pt~(II) Rectangular Metallomacrocycles: A Comparative Study of their Inclusion Complexes
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Synthesis of New Self-assembled Pd~(II) and Pt~(II) Rectangular Metallomacrocycles: A Comparative Study of their Inclusion Complexes

机译：新的自组装Pd〜（II）和Pt〜（II）矩形金属大环化合物的合成：其包合物的比较研究

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摘要

New palladium and platinum metallocycles have been synthesized by reacting 4,4'-bipyridinium-based li-gands with Pd~(II) and Pt~(II) complexes. Strict thermodynamic self-assembly of 1 and [M(en)(NO3)2] (M=Pd, Pt) 6a,b afforded metallocycles 7a,b. However, the synthesis of 8 a,b and 9 a,b required a self-assembly process that used sodium p-phenylenediacetate (12) as a template. Finally, metallocycles 10 a,b were synthesized under high dilution conditions from ligand 4. The formation of inclusion complexes betweenmetallocycles 7-10 and substrates 13 and 14 were studied by low-temperature ~1H NMR, and the association constants were determined in nitrometh-ane and water by following the characteristic charge-transfer band that these metallomacrocycles show in their UV-visible absorption spectra. A clear correlation between the affinity for a sub-strate and the dimensions of the metal-locycle was observed. Metallocycles 8 b and 9 b exhibited the highest binding constants in water and nitromethane. This observation is in agreement with the DFT (B3LYP)-optimized geometries obtained for the different metallomacrocycles, which indicate that only macrocycles 8 and 9 possess a cavity with a width larger than 3.5 A. The insertion of hydroquinone or diol 13 into the cavity of metallocycle 11a was confirmed by single-crystal X-ray crystallography.
机译：通过使4,4'-联吡啶鎓基的Li-gand与Pd〜（II）和Pt〜（II）配合物反应合成了新的钯和铂金属环。 1和[M（en）（NO3）2]（M = Pd，Pt）6a，b的严格热力学自组装提供了金属环7a，b。但是，合成8a，b和9a，b需要使用对苯二乙酸钠（12）作为模板的自组装过程。最后，在高稀释条件下由配体4合成了金属环10a，b。通过低温〜1H NMR研究了金属环7-10与底物13和14之间的包合物，并在亚硝基甲基通过遵循这些金属大环化合物在其紫外可见吸收光谱中显示的特征性电荷转移带来确定水和烷烃之间的关系。观察到对底物的亲和力与金属环的尺寸之间存在明显的相关性。金属环8b和9b在水和硝基甲烷中表现出最高的结合常数。该观察结果与针对不同的金属大环化合物获得的DFT（B3LYP）优化几何结构吻合，后者表明只有大环8和9的腔体的宽度大于3.5A。氢醌或二醇13插入到大分子环的腔体中。通过单晶X射线晶体学确认了金属环11a。

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