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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >An integrated X-ray and molecular dynamics study of uranyl-salen structures and properties
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An integrated X-ray and molecular dynamics study of uranyl-salen structures and properties

机译：铀酰-salen的结构和性质的综合X射线和分子动力学研究

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摘要

Uranium complexes of bis(p-tert-butyl-salicylidene)-1,2- diphenylethylenediamine (1) and bis(salicylidene)-1,2-diphenylethylenediamine (2) have been synthesized and investigated by X-ray single crystal diffraction and MD calculations in Periodic Boundary Conditions. Both compounds form crystals which are densely packed and do not provide voids accessible to solvent molecules. The configurations adopted by 1 and 2 are determined by well defined T-shaped and π-stacking non covalent interactions between phenyl groups of adjacent molecules as well as by a network of hydrogen bonds. These interactions and the relative arrangements of the molecules, explain the packing in the crystal structures. Each uranyl moiety shows a penta-coordination in the equatorial plane perpendicular to the trans oxygens giving rise, in both compounds, to a bypiramidal geometry. As usual for this class of compounds, the 5th position is characterized by the presence of the coordinated solvent. The in silico simulations confirm this hypothesis in very fine details. Moreover, in 1, even the partial occupancy of the solvent molecule determined from the crystal structure refinement, was shown to be due to a constrained freedom of motion of the solvent molecule that can be reproduced by molecular dynamics. This suggests that the reported disorder is not due to a poor quality of the harvested crystals but to a structural feature. In further agreement with the above mentioned results, DFT calculations demonstrated that the molecular orbital configuration and energies suit the described properties of complexes 1 and 2 suggesting a potential enantioselective activity as already shown by molecules belonging to this class of compounds.
机译：合成了双（对叔丁基-水杨基亚烷基）-1,2-二苯基乙二胺（1）和双（水杨基）-1,2-二苯基乙二胺（2）的铀络合物并通过X射线单晶衍射和MD研究周期边界条件中的计算。两种化合物均形成紧密堆积的晶体，并且不会提供溶剂分子可及的空隙。 1和2所采用的构型是由相邻分子的苯基之间明确定义的T形和π堆积非共价相互作用以及氢键网络决定的。这些相互作用和分子的相对排列解释了晶体结构中的堆积。每个铀酰部分在垂直于反式氧的赤道平面上均表现出五配位，从而在两种化合物中都产生了吡锥体结构。与这类化合物一样，第五位的特征是配位溶剂的存在。计算机模拟非常详细地证实了这一假设。此外，在图1中，甚至显示出由晶体结构的细化确定的溶剂分子的部分占有是由于溶剂分子的运动自由度受约束而可以通过分子动力学再现的。这表明所报道的病症不是由于所收获晶体的质量差，而是由于结构特征。与上述结果进一步吻合，DFT计算证明分子轨道构型和能量适合于配合物1和2的描述的性质，表明潜在的对映选择性活性已被属于此类化合物的分子所显示。

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