清华大学王泉明团队报道了簇后共价修饰和客致刺激响应发光构建的簇结构笼。相关研究成果于2024年5月7日发表在《德国应用化学》。

通过用三氨基三乙胺对六醛簇前体进行簇后共价修饰，构建了一种新型的基于金（I）簇的双笼。簇结构上的笼具有双腔和四个结合位点，显示出对银（I）和铜（I）客体的位点辨别性结合。三角帽中的客体影响簇的发光：四银（I）主客体复合物是弱的红色发光，而双铜(I)-双银(I)是非发光的，但是刺激响应的超分子。三亚胺腔内的铜（I）离子对氧化敏感，这使得H₂O₂溶液能够触发明亮的发射前体簇的释放。

将簇与空腔杂交以构建基于簇的笼为功能簇设计提供了一个创新概念，簇后共价修饰开辟了微调簇性质的新途径。

附：英文原文

Title: A Cages-on-Cluster Structure Constructed by Post-Clustering Covalent Modifications and Guest-Enabled Stimuli-Responsive Luminescence

Author: Yang Yang, Shan Guo, Qian Zhang, Zong-Jie Guan, Quan-Ming Wang

Issue&Volume: 2024-05-07

Abstract: A novel gold(I)-cluster-based twin-cage is constructed by post-clustering covalent modification of a hexa-aldehyde cluster precursor with triaminotriethylamines. The cages-on-cluster structure have double cavities and four binding sites, showing site discriminative binding for silver(I) and copper(I) guests. The guests in the tripodal hats affect the luminescence of the cluster: tetra-silver(I) host-guest complex is weak red emissive, while bis-copper(I)-bis-silver(I) one is non-emissive but a stimuli-responsive supramolecule. The copper(I) ion inside the tri-imine cavity is oxidation sensitive, which enable the release of the bright emissive precursor cluster triggered by H2O2 solution. The hybridization of a cluster with cavities to construct a cluster-based cage presents an innovative concept for functional cluster design, and the post-clustering covalent modification opens up new avenues of finely tuning the properties of clusters.

DOI: 10.1002/anie.202404798

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202404798