Li Yingwei, Stec Grant J, Kim Hong Ki, Thapa Surendra, Zheng Shao-Liang, McClelland Arthur, Mason Jarad A
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA.
Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, USA.
Nat Chem. 2025 Feb;17(2):169-176. doi: 10.1038/s41557-024-01696-6. Epub 2025 Jan 8.
Atomically precise nanoclusters can be assembled into ordered superlattices with unique electronic, magnetic, optical and catalytic properties. The co-crystallization of nanoclusters with functional organic molecules provides opportunities to access an even wider range of structures and properties, but can be challenging to control synthetically. Here we introduce a supramolecular approach to direct the assembly of atomically precise silver nanoclusters into a series of nanocluster‒organic ionic co-crystals with tunable structures and properties. By leveraging non-covalent interactions between anionic silver nanoclusters and cationic organic macrocycles of varying sizes, the orientation of nanocluster surface ligands can be manipulated to achieve in situ resolution of enantiopure nanocluster‒organic ionic co-crystals that feature large chiroptical effects. Beyond chirality, this co-crystal assembly approach provides a promising platform for designing functional solid-state nanomaterials through a combination of supramolecular chemistry and atomically precise nanochemistry.
原子精确的纳米团簇可以组装成具有独特电子、磁性、光学和催化性质的有序超晶格。纳米团簇与功能性有机分子的共结晶为获得更广泛的结构和性质提供了机会，但在合成控制方面可能具有挑战性。在这里，我们引入了一种超分子方法，将原子精确的银纳米团簇组装成一系列具有可调结构和性质的纳米团簇-有机离子共晶体。通过利用阴离子银纳米团簇与不同大小的阳离子有机大环之间的非共价相互作用，可以操纵纳米团簇表面配体的取向，以实现具有大的手性光学效应的对映体纯纳米团簇-有机离子共晶体的原位拆分。除了手性之外，这种共晶体组装方法通过超分子化学和原子精确的纳米化学相结合，为设计功能性固态纳米材料提供了一个有前景的平台。
