Abstract With the aim to explore the electronic structure and the influence of halogen bonds to the supramolecular networks of lanthanide Schiff base complexes, halogenated salen-type Schiff-base and cerium nitrate were chosen as starting materials and isolated a new salen-type cerium(IV) complex [CeIV(3,5Br-salpn)2] (1) where 3,5Br-salpn = N,N’-bis(3,5‑bromo salicylidene)-1,3-diaminopropane. The complex was investigated in the solid state by single-crystal X-ray diffraction. Structural analysis reveal the substitutional halogen atoms play an important role in tuning the molecule structure and supramolecular networks. The electronic structure of halogen bonds was confirmed by theoretical calculation, which uncovered an interesting phenomenon that the σ-hole of bromine atoms of different substituents present quite different molecular electrostatic surface potential (5-Br: Vmax = 6.8 kcal/mol and 3-Br: Vmax = 13.2 kcal/mol). Hirshfeld surface analysis showed that bromine atoms involved intermolecular contacts donate 56.6% contribution of all the interactions, indicating the significant role of bromine atoms in crystal structures. Additionally, fluorescence experiments proved that the halogenated ligand has an important influence on the fluorescence behavior of the complex.

中文翻译：

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多卤化镧系元素席夫碱配合物的晶体和电子结构：从结构和理论分析中洞察卤素键

摘要 为探索电子结构及卤键对镧系元素席夫碱配合物超分子网络的影响，以卤代赛伦型席夫碱和硝酸铈为起始原料，分离出一种新型的赛伦型铈(IV)。 ) 复合物 [CeIV(3,5Br-salpn)2] (1) 其中 3,5Br-salpn = N,N'-双（3,5-溴水杨烯）-1,3-二氨基丙烷。通过单晶 X 射线衍射在固态下研究该配合物。结构分析表明，取代卤素原子在调节分子结构和超分子网络方面起着重要作用。卤素键的电子结构经理论计算证实，这揭示了一个有趣的现象，即不同取代基的溴原子的 σ-hole 呈现出截然不同的分子静电表面电位（5-Br：Vmax = 6.8 kcal/mol 和 3-Br：Vmax = 13.2 kcal/mol）。Hirshfeld 表面分析表明，涉及分子间接触的溴原子贡献了所有相互作用的 56.6%，表明溴原子在晶体结构中的重要作用。此外，荧光实验证明卤化配体对配合物的荧光行为有重要影响。表明溴原子在晶体结构中的重要作用。此外，荧光实验证明卤化配体对配合物的荧光行为有重要影响。表明溴原子在晶体结构中的重要作用。此外，荧光实验证明卤化配体对配合物的荧光行为有重要影响。