Ultra-High Metal-Ion Selectivity Induced by Intramolecular Cation-π Interactions for the One-Pot Synthesis of Precise...

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 Zn₂Cu₄L3₄ 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 ZnL1₂ and Cu₂L2₂ 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 Zn₂Cu₄L3₄, 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.