Ultra‐High Metal‐Ion Selectivity Induced by Intramolecular Cation‐π Interactions for the One‐Pot Synthesis of Precise Heterometallic Architectures
Junjuan Shi, Kehuan Li, Hao Yu, Ningxu Han, Tianyi Yang, Xin Jiang, Xin‐Qi Hao, Zhi Chen, Guanglu Wu, Houyu Zhang, Bingling Li, Ming Wang
Abstract
Abstract Heterometallic supramolecules, known for their unique synergistic effects, have shown broad applications in photochemistry, host‐guest chemistry, and catalysis. However, there are great challenges to precisely construct heterometallic supramolecules rather than a statistical mixture, due to the limited metal‐ion selectivity of coordination units. In particular, heterometallic architectures precisely encoded with different metal ions usually fail to form in a one‐pot method when only one type of coordinated motif exists due to its poor metal‐ion selectivity. Herein, we propose an effective intramolecular cation‐π (ICπ) strategy and successfully constructed the heterometallic supramolecule Zn 2 Cu 4 L3 4 by the one‐pot self‐assembly of tritopic terpyridyl ligand L3 with Zn(II) and Cu(II), following a clear self‐assembly mechanism in which only thermodynamic dimers ZnL1 2 and Cu 2 L2 2 were constructed with model ligands L1 , L2 , Zn(II) and Cu(II) with perfect self‐sorting and an ultra‐high metal‐selectivity feature. The successful construction of the heterometallic supramolecule Zn 2 Cu 4 L3 4 , in which the definite sequence of metal ions Zn(II) and Cu(II) is encoded in the one‐pot method, will offer a novel approach to precisely construct heterometallic architectures.