Abstract

We report a synthesis of a series of molecular compounds and coordination polymers of Zn²⁺, Mn²⁺ Cd²⁺, Eu³⁺, and Tb³⁺ with 4-allyl-2,3,5,6-tetrafluorobenzoic acid (4-Afb) anions and 1,10-phenanthroline with compositions [Zn(H₂O)(phen)(4-Afb)₂] (1), [Mn(H₂O)(phen)(4-Afb)₂]_n·nH₂O (2), [Cd(H₂O)(phen)(4-Afb)₂]_n (3), [Cd(phen)(4-Afb)₂]_n (4), [Ln₂(phen)₂(4-Afb)₆] (Ln = Eu 5Eu; Tb 5Tb). It is shown that the obtained cadmium coordination polymers have various compositions and structures, depending on crystallization conditions. The prepared compounds are characterized by single-crystal XRD, powder XRD, IR spectroscopy, and CHN analysis. Noncovalent interactions are analyzed using the Hirshfeld surface analysis. It is determined that the crystal packings is mainly stabilized by π⋯π, C–H⋯F, and C–F⋯π interactions. The photoluminescent properties of the 5Eu and 5Tb complexes are studied. It is shown that the structure-forming effects of non-covalent “arene–perfluoroarene” interactions can be possibly used for preorganizing reactive functional groups in the crystal.

中文翻译：

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Zn2+、Mn2+、Cd2+、Eu3+ 和 Tb3+ 与 4-烯丙基-2,3,5,6-四氟苯甲酸阴离子和 1,10-菲咯啉配合物的合成、结构和光致发光性能

摘要

我们报道了 Zn ²⁺、Mn ²⁺ Cd ²⁺、Eu ³⁺和 Tb ³⁺与 4-烯丙基-2,3,5,6-四氟苯甲酸（4 -Afb) 阴离子和 1,10-菲咯啉，其组成为 [Zn(H ₂ O)(phen)(4-Afb) ₂ ] ( 1 )、[Mn(H ₂ O)(phen)(4-Afb) ₂ ] _n · n H ₂ O ( 2 ), [Cd(H ₂ O)(phen)(4-Afb) ₂ ] _n ( 3 ), [Cd(phen)(4-Afb) ₂ ] _n ( 4 ), [ Ln ₂ (phen) ₂ (4-Afb) ₆ ] (Ln = Eu 5Eu；Tb 5Tb )。结果表明，根据结晶条件，所得镉配位聚合物具有不同的组成和结构。通过单晶 XRD、粉末 XRD、红外光谱和 CHN 分析对所制备的化合物进行了表征。使用赫什菲尔德表面分析来分析非共价相互作用。确定晶体堆积主要通过π⋯π、C-H⋯F和C-F⋯π相互作用来稳定。研究了5Eu和5Tb配合物的光致发光性质。结果表明，非共价“芳烃-全氟芳烃”相互作用的结构形成效应可能可用于预组织晶体中的反应性官能团。