Constructing Ultrastable Metallo-Cages via <i>In Situ</i> Deprotonation/Oxidation of Dynamic Supramolecular Assemblies
Pingru Su, Wenjing Zhang, Chenxing Guo, Hong Liu, Chuanhong Xiong, Runxu Tang, Chuanxin He, Zhi Chen, Xiujun Yu, Heng Wang, Xiaopeng Li
Abstract
Coordination-driven self-assembly enables the spontaneous construction of metallo-supramolecules with high precision, facilitated by dynamic and reversible metal–ligand interactions. The dynamic nature of coordination, however, results in structural lability in many metallo-supramolecular assembly systems. Consequently, it remains a formidable challenge to achieve self-assembly reversibility and structural stability simultaneously in metallo-supramolecular systems. To tackle this issue, herein, we incorporate an acid-/base-responsive tridentate ligand into multitopic building blocks to precisely construct a series of metallo-supramolecular cages through coordination-driven self-assembly. These dynamic cagelike assemblies can be transformed to their static states through mild in situ deprotonation/oxidation, leading to ultrastable skeletons that can withstand high temperatures, metal ion chelators, and strong acid/base conditions. This in situ transformation provides a reliable and powerful approach to manipulate the kinetic features and stability of metallo-supramolecules and allows for modulation of encapsulation and release behaviors of metallo-cages when utilizing nanoscale quantum dots (QDs) as guest molecules.