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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Molecular modelling of Jahn-Teller distortions in Cu(II)N-6 complexes: elongations, compressions and the pathways in between
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Molecular modelling of Jahn-Teller distortions in Cu(II)N-6 complexes: elongations, compressions and the pathways in between

机译：Cu（II）N-6配合物Jahn-Teller畸变的分子模型：伸长，压缩及其之间的途径

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摘要

Ligand Field Molecular Mechanics (LFMM) parameters have been optimised for six-coordinate Cu(II) complexes containing amine, pyridine, imidazole and pyrazine donors. As found in previous LFMM applications, the new parameters automatically generate distorted structures with the magnitudes of the Jahn-Teller elongations in good agreement with experiment. Here, we explore the rest of the potential energy surface. The introduction of axial strain drives the LFMM structures via rhombic geometries to the compressed structure, the latter corresponding to the saddle point between successive elongation axes. Calculated barrier heights between compressed and elongated geometries also agree well with available experimental data. In every case bar one, the LFMM predicts that the crystallographically observed elongation axis corresponds to the overall lowest energy well. The structural predictions are confirmed by independent density functional theory (DFT) optimisations. LFMM calculations on bis(2,5-pyrazolylpyridine)copper complexes display a smooth variation in structure as a function of pyrazolyl substituent from elongated for R = H through to fully compressed for R = Bu-t. This behaviour is driven by the steric interactions with the ground state varying smoothly as a linear combination of {d(x2-y2)}(1) and {d(z2)}(1).
机译：配体场分子力学（LFMM）参数已针对包含胺，吡啶，咪唑和吡嗪供体的六配位Cu（II）配合物进行了优化。如以前的LFMM应用中所发现的那样，新参数会自动生成变形的结构，其变形的Jahn-Teller伸长量与实验吻合良好。在这里，我们探索其余的势能面。轴向应变的引入通过菱形几何将LFMM结构驱动到压缩结构，该压缩结构对应于连续伸长轴之间的鞍点。压缩几何形状和细长几何形状之间的势垒高度计算值也与可用的实验数据非常吻合。在每种情况下，LFMM都会预测晶体学上观察到的伸长轴对应于总体最低能量阱。结构预测得到独立密度泛函理论（DFT）优化的证实。对双（2,5-吡唑基吡啶）铜配合物的LFMM计算显示结构上的平稳变化是吡唑基取代基的函数，从R = H延长到R = Bu-t完全压缩。这种行为是由与基态平稳相互作用的空间相互作用驱动的，基态以{d（x2-y2）}（1）和{d（z2）}（1）的线性组合平滑变化。

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