Ultra‐High Metal‐Ion Selectivity Induced by Intramolecular Cation‐π Interactions for the One‐Pot Synthesis of Precise Heterometallic Architectures

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 statistical mixture, due to the limited metal‐ions selectivity of coordination units. Especially, heterometallic architectures precisely encoding with different metal ions usually fail to obtain in one‐pot method when only one type of coordinated motif exists due to its poor metal‐ion selectivity. Herein, we proposed an effective intramolecular cation‐π (ICπ) strategy and successfully constructed the heterometallic supramolecule Zn2Cu4L34 by one‐pot self‐assembly of tritopic terpyridyl ligand L3 with Zn(II) and Cu(II), following the clear self‐assembly mechanism that only thermodynamic dimers ZnL12 and Cu2L22 were constructed with model ligands L1, L2, Zn(II) and Cu(II) with perfect self‐sorting and ultra‐high metal‐selectivity feature. The successful construction of the heterometallic supramolecule Zn2Cu4L34, encoding the definite sequence of metal ions Zn(II) and Cu(II) in one‐pot method, will offer a novel approach to precisely construct heterometallic architectures.