Effects of Metal Cations and Counter Anions on the Structural Stability of Isoquinoline‐Based Metallo‐Supramolecular Cages

Comprehensive Summary Metallo‐supramolecular architectures that are constructed by coordination‐driven self‐assembly have received tremendous attention on account of their diverse yet molecular‐level precise structures and broad applications. Of particular, metal cations and counter anions are fundamentally important in terms of self‐assembly, characterization and property; however, their effects on the structural stabilities of metallo‐supramolecular architectures have seldom been investigated. To address this issue, herein, a series of octahedral metallo‐cages that are capable of tolerating with five metal cations (Pd 2+ , Cu 2+ , Ni 2+ , Co 2+ and Zn 2+ ), and five counter anions (ClO 4 – , OTf – , BF 4 – , NTf 2 – and NO 3 – ) are constructed by the coordination‐driven self‐assembly of a well‐designed tritopic isoquinoline‐based ligand with corresponding metal salts. Structural stability studies show that metal cations and counter anions play a critical role in the stability of the resulting cages depending on their coordination abilities and stacking manners. This work provides deep insights in the ever‐diversifying field of metallo‐supramolecular chemistry, and will enable us to design more sophisticated assembled structure with desired function.