近日，西北大学韩英锋团队通过线性d₁₀ AgI/AuI-NHC配位工程实现Lemnisular金属环的立体构建。这一研究成果发表在2025年7月14日出版的《中国化学》杂志上。

螺旋扭曲的分子结构是生物学和合成超分子化学中的关键基序，其独特的功能特性源于其手性几何形状。尽管具有非接触交叉点的lemniscular大环引起了越来越多的兴趣，但它们的金属超分子类似物仍未得到充分探索，这主要是因为合成挑战阻碍了精确控制。

研究组报告了一种利用含N-杂环碳（NHC）配体的AgI和AuI配合物的线性配位几何结构来控制构建lemniscular金属环的配位驱动策略。该方法的关键是设计含有螺旋烯基团的双NHC咪唑配体，促进螺旋烯的同手性二聚化，抑制非交叉大环的形成。

通过该方法合成了AgI和AuI-NHC外环结构，并通过多种合成途径对AuI配合物进行了验证。通过电喷雾电离质谱、紫外-可见吸收和荧光发射光谱、X射线晶体学和密度泛函理论计算对生成的结构进行了表征，证实了目标金属环的形成。值得注意的是，这项工作解决了金属超分子韧带系统长期缺乏的问题，增加了大环的结构多样性，并为这些复合物的紧急功能的系统研究建立了一个平台。

附：英文原文

Title: Stereodirected Construction of Lemniscular Metallacycles via Linear d10 AgI/AuI–NHC Coordination Engineering

Author: Meng-Zhi Han, Hai-Ning Zhang, Le Zhang, Xiang-Yang Li, Can Chen, Ying-Feng Han

Issue&Volume: 2025-07-14

Abstract: Helically twisted molecular architectures are critical motifs in both biology and synthetic supramolecular chemistry, with unique functional properties derived from their chiral geometries. Although lemniscular (figure-eight) macrocycles with a noncontact crossover point have attracted increasing interest, their metallosupramolecular analogs remain underexplored, largely because of synthetic challenges that hinder precise control. Herein, we report a coordination-driven strategy for the controlled construction of lemniscular metallacycles by exploiting the linear coordination geometry of AgI and AuI complexes containing N-heterocyclic carbene (NHC) ligands. The key to this approach is the design of a bis-NHC imidazolium ligand containing helicene moieties, which promotes homochiral helicene dimerization and suppresses noncrossover macrocycle formation. AgI and AuI–NHC lemniscular architectures were synthesized via this method, and the AuI complex was validated through multiple synthetic pathways. The generated structures were characterized via electrospray ionization mass spectrometry, ultraviolet–visible absorption and fluorescence emission spectroscopy, X-ray crystallography, and density functional theory calculations, confirming the formation of the target metallacycles. Notably, this work addresses the long-standing scarcity of metallosupramolecular lemniscular systems, increases the structural diversity of macrocycles, and establishes a platform for the systematic investigation of the emergent functionalities of these complexes.

DOI: 10.1002/cjoc.70178

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70178