香港大学任詠华团队报道了多核金(I)硫配合物从团簇和笼形到大环的演化。相关研究成果发表在2023年12月28日出版的《美国化学会杂志》。

利用精心设计的双齿膦配体，构建了两个前所未有的具有不同温度诱导的刺激响应行为和发射性质的，四碳五核和四碳三核金（I）硫化物簇（分别表示为Au₃₄LMe和Au₂₄LCbz）。Au₃₄LMe代表分子中具有1000多个原子的金（I）亚磺酰基簇的最高核性。首次组装了基于金属簇节点的八角形大环。

通过¹H和³¹P{¹H}NMR光谱监测了自组装和温度诱导的刺激响应过程，并通过单晶结构分析和高分辨率电喷雾电离质谱数据确定了离散金（I）配合物的身份。取代基对V形1，3-双（二苯基膦）苯配体施加的空间效应已被证明，控制了从1D簇和3D笼到2D大环的自组装。

该项工作不仅为构建和调节2D大环金（I）亚磺酰配合物的结构提供了一种新的策略，而且为未来更高多边形和簇节点大环的精确设计和控制构建奠定了基础。

附：英文原文

Title: Evolution of Polynuclear Gold(I) Sulfido Complexes from Clusters and Cages to Macrocycles

Author: Liang-Liang Yan, Vivian Wing-Wah Yam

Issue&Volume: December 28, 2023

Abstract: Two unprecedented tetratriacontanuclear and tetraicosanuclear gold(I) sulfido clusters (denoted as Au34-LMe and Au24-LCbz) with different temperature-induced stimulus-responsive behavior and emission property have been constructed by taking advantage of the judiciously designed bidentate phosphine ligand. Au34-LMe represents the highest nuclearity of the gold(I) sulfido cluster with more than a thousand atoms in the molecule. Octagonal macrocycles based on metal-cluster nodes have been assembled for the first time. The self-assembly and temperature-induced stimulus-responsive processes were monitored by 1H and 31P{1H} NMR spectroscopy, and the identities of the discrete gold(I) complexes were established by single-crystal structural analysis and high-resolution electrospray ionization mass spectrometry data. The steric effects exerted by the substituents on the V-shaped 1,3-bis(diphenylphosphino)benzene ligand have been shown to govern the self-assembly from the 1D cluster and 3D cage to 2D macrocycles. This work not only offers a new strategy to construct and regulate the structure of 2D macrocyclic gold(I) sulfido complexes but also lays the foundation for the future precise design and controlled construction of higher polygonal and cluster-node macrocycles.

DOI: 10.1021/jacs.3c10381

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.3c10381