Shi Junjuan, Li Kehuan, Yu Hao, Han Ningxu, Yang Tianyi, Jiang Xin, Hao Xin-Qi, Chen Zhi, Wu Guanglu, Zhang Houyu, Li Bingling, Wang Ming
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, Jilin, 130012, China.
School of Materials Science and Engineering, Nanyang Technological University, 637553, Singapore.
Angew Chem Int Ed Engl. 2025 Jan 21;64(4):e202416150. doi: 10.1002/anie.202416150. Epub 2024 Nov 5.
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 ZnCuL3 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 and CuL2 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 ZnCuL3, 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.
异金属超分子以其独特的协同效应而闻名，在光化学、主客体化学和催化领域展现出广泛的应用。然而，由于配位单元的金属离子选择性有限，精确构建异金属超分子而非统计混合物面临巨大挑战。特别是，当仅存在一种类型的配位基序时，由于其金属离子选择性较差，通常无法通过一锅法形成精确编码有不同金属离子的异金属结构。在此，我们提出一种有效的分子内阳离子-π（ICπ）策略，并通过三齿三联吡啶配体L3与Zn(II)和Cu(II)的一锅自组装成功构建了异金属超分子ZnCuL3，遵循明确的自组装机制，其中仅用模型配体L1、L2、Zn(II)和Cu(II)构建了具有完美自分类和超高金属选择性特征的热力学二聚体ZnL1和CuL2。异金属超分子ZnCuL3的成功构建，其中金属离子Zn(II)和Cu(II)的确定序列通过一锅法编码，将为精确构建异金属结构提供一种新方法。
