Cu(II) 配位化合物中涉及阴离子–π/π–π/阴离子–π 组装和非常规 Cl⋯Cl 相互作用的协同三元组装：实验和理论研究,Crystals

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Cu(II) 配位化合物中涉及阴离子–π/π–π/阴离子–π 组装和非常规 Cl⋯Cl 相互作用的协同三元组装：实验和理论研究
Crystals ( IF 2.4 ) Pub Date : 2023-03-17 , DOI: 10.3390/cryst13030517
Pinku Sarma ₁ , Rosa M. Gomila ₂ , Antonio Frontera ₂ , Miquel Barcelo-Oliver ₂ , Manjit K. Bhattacharyya ₁

Affiliation

Cu(II) 的两种配位化合物，即 [Cu (phen)2Cl](NO3)·H2O（化合物 1）和 [Cu2(µ-Cl2)Cl2(Hdmpz)4]（化合物 2），其中 phen = 1 ,10-菲咯啉和 Hdmpz = 3,5-二甲基吡唑在室温下合成，并使用元素分析、TGA、光谱技术（FT-IR 和电子）和单晶 X 射线衍射研究进行表征。涉及配位苯基的协同阴离子-π/π-π/阴离子-π 组装，以及未配位的硝酸盐部分，在稳定化合物 1 的晶体结构中起着关键作用。非常规 I 型 Cl⋯Cl 相互作用涉及配位Cl 原子增强了化合物 2 的晶体结构。我们使用 DFT 计算从理论上探索了在化合物 1 和 2 的晶体结构中观察到的超分子组装，MEP 表面分析和组合 NCI 图/QTAIM 计算工具。理论分析表明，化合物1中的反平行π-堆叠相互作用和化合物2中的N-H···Cl氢键是稳定化合物的强结构导向非共价合成子。在化合物 1 中观察到的阴离子-π/π-π/阴离子-π 组装中，阴离子-π 相互作用通过降低金属配位缺电子苯环之间的静电排斥力增强了 π 堆积。

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Cooperative Ternary Assemblies Involving Anion–π/π–π/Anion–π Assemblies and Unconventional Cl⋯Cl Interactions in Cu(II) Coordination Compounds: Experimental and Theoretical Studies

Two coordination compounds of Cu(II), namely, [Cu (phen)2Cl](NO3)·H2O (compound 1) and [Cu2(µ-Cl2)Cl2(Hdmpz)4] (compound 2), where phen = 1,10-phenanthroline and Hdmpz = 3,5-dimethylpyrazole, were synthesized at room temperature and characterized using elemental analysis, TGA, spectroscopic techniques (FT-IR and electronic) and single-crystal X-ray diffraction studies. The cooperative anion–π/π–π/anion–π assemblies involving the coordinated phen, along with the uncoordinated nitrate moieties, played pivotal roles in the stabilization of the crystal structure of compound 1. Unconventional type I Cl⋯Cl interactions involving the coordinated Cl atoms provided reinforcement to the crystal structure of compound 2. We theoretically explored the supramolecular assemblies observed in the crystal structures of compounds 1 and 2 using DFT calculations, MEP surface analysis and combined NCI plot/QTAIM computational tools. Theoretical analysis revealed that the antiparallel π-stacking interactions in compound 1 and the N–H···Cl H-bonds in compound 2 were the strong structure-guiding non-covalent synthons which stabilized the compounds. In the anion–π/π–π/anion–π assembly observed in compound 1, the anion–π interaction reinforced the π-stacking by reducing the electrostatic repulsion between the metal-coordinated electron-deficient phen rings.

更新日期：2023-03-17

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