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

Author:

Yang Yang12,Guo Shan1,Zhang Qian1,Guan Zong‐Jie32,Wang Quan‐Ming32ORCID

Affiliation:

1. Department of Chemistry, College of Chemistry and Materials Science Jiangsu Normal University Xuzhou 221116 P. R. China

2. Department of Chemistry, School of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 P. R. China

3. Department of Chemistry Tsinghua University Beijing 100084 P. R. China

Abstract

AbstractA gold(I)‐cluster‐based twin‐cage has been constructed by post‐clustering covalent modification of a hexa‐aldehyde cluster precursor with triaminotriethylamines. The cages‐on‐cluster structure has double cavities and four binding sites, which show site‐discriminative binding for silver(I) and copper(I) guests. The guests in the tripodal hats affect the luminescence of the cluster: the tetra‐silver(I) host–guest complex is weakly red‐emissive, while the bis‐copper(I)‐bis‐silver(I) one is non‐emissive but is a stimuli‐responsive supramolecule. The copper(I) ion inside the tri‐imine cavity is oxidation sensitive, which enables 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 for finely tuning the properties of clusters.

Funder

National Natural Science Foundation of China

Publisher

Wiley

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