Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, Tomsk 634050, Russia.
Institute of Chemistry, Saint Petersburg State University, Saint Petersburg 199034, Russia.
Int J Mol Sci. 2023 Sep 27;24(19):14642. doi: 10.3390/ijms241914642.
We designed 0D, 1D, and 2D supramolecular assemblies made of diaryliodonium salts (functioning as double σ-hole donors) and carboxylates (as σ-hole acceptors). The association was based on two charge-supported halogen bonds (XB), which occurred between I sites of the iodonium cations and the carboxylate anions. The sequential introduction of the carboxylic groups in the aryl ring of the benzoic acid added a dimension to the 0D supramolecular organization of the benzoate, which furnished 1D-chained and 2D-layered structures when terephthalate and trimesate anions, correspondingly, were applied as XB acceptors. The structure-directing XB were studied using DFT calculations under periodic boundary conditions and were followed by the one-electron-potential analysis and the Bader atoms-in-molecules topological analysis of electron density. These theoretical methods confirmed the existence of the XB and verified the philicities of the interaction partners in the designed solid-state structures.
我们设计了由二芳基碘鎓盐（作为双 σ-hole 供体）和羧酸盐（作为 σ-hole 受体）组成的 0D、1D 和 2D 超分子组装体。这种结合基于两个电荷支持的卤键（XB），它发生在碘鎓阳离子的 I 位和羧酸盐阴离子之间。苯甲酸的芳环中连续引入羧酸基团，为苯甲酸的 0D 超分子结构增加了一个维度，当对苯二甲酸和均苯三甲酸阴离子分别作为 XB 受体时，提供了 1D 链式和 2D 层状结构。使用周期性边界条件下的 DFT 计算研究了结构导向的 XB，并进行了单电子势分析和电子密度的 Bader 原子在分子拓扑分析。这些理论方法证实了 XB 的存在，并验证了设计的固态结构中相互作用体的亲合力。
