Halogen bonding is a highly directional interaction and a potential tool in functional material design through self-assembly. Herein, we describe two fundamental supramolecular strategies to synthesize molecularly imprinted polymers (MIPs) with halogen bonding-based molecular recognition sites. In the first method, the size of the σ-hole was increased by aromatic fluorine substitution of the template molecule, enhancing the halogen bonding in the supramolecule. The second method involved sandwiching hydrogen atoms of a template molecule between iodo substituents, which suppressed competing hydrogen bonding and enabled multiple recognition patterns, improving the selectivity. The interaction mode between the functional monomer and the templates was elucidated by ¹H NMR, ¹³C NMR, X-ray absorption spectroscopy, and computational simulation. Finally, we succeeded in the effective chromatographic separation of diiodobenzene isomers on the uniformly sized MIPs prepared by multi-step swelling and polymerization. The MIPs selectively recognized halogenated thyroid hormones via halogen bonding and could be applied to screening endocrine disruptors.

中文翻译：

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通过卤素键合的合理超分子策略，有效识别分子印迹中的卤素

卤素键合是一种高度定向的相互作用，是通过自组装进行功能材料设计的潜在工具。在这里，我们描述了两种基本的超分子策略来合成具有基于卤素键的分子识别位点的分子印迹聚合物（MIP）。在第一种方法中，通过模板分子的芳族氟取代来增加σ孔的尺寸，增强超分子中的卤素键合。第二种方法是将模板分子的氢原子夹在碘取代基之间，这抑制了竞争性氢键并实现了多种识别模式，从而提高了选择性。^通过1 H NMR阐明了功能单体和模板之间的相互作用模式，¹³13C NMR、X 射线吸收光谱和计算模拟。最后，我们在通过多步溶胀和聚合制备的均匀尺寸的MIP上成功地对二碘苯异构体进行了有效的色谱分离。MIP 通过卤素键选择性识别卤化甲状腺激素，可用于筛选内分泌干扰物。