Atomically precise organomimetic cluster nanomolecules assembled via perfluoroaryl-thiol SNAr chemistry

作者：Qian Elaine A; Wixtrom Alex I; Axtell Jonathan C; Saebi Azin; Jung Dahee; Rehak Pavel; Han Yanxiao; Moully Elamar Hakim; Mosallaei Daniel; Chow Sylvia; Messina Marco S; Wang Jing Yang; Royappa A Timothy; Rheingold Arnold L; Maynard Heather D; Kral Petr; Spokoyny Alexander M^*

来源：Nature Chemistry, 2017, 9(4): 333-340.

DOI：10.1038/NCHEM.2686

The majority of biomolecules are intrinsically atomically precise, an important characteristic that enables rational engineering of their recognition and binding properties. However, imparting a similar precision to hybrid nanoparticles has been challenging because of the inherent limitations of existing chemical methods and building blocks. Here we report a new approach to form atomically precise and highly tunable hybrid nanomolecules with well-defined three-dimensionality. Perfunctionalization of atomically precise clusters with pentafluoroaryl-terminated linkers produces size-tunable rigid cluster nanomolecules. These species are amenable to facile modification with a variety of thiol-containing molecules and macromolecules. Assembly proceeds at room temperature within hours under mild conditions, and the resulting nanomolecules exhibit high stabilities because of their full covalency. We further demonstrate how these nanomolecules grafted with saccharides can exhibit dramatically improved binding affinity towards a protein. Ultimately, the developed strategy allows the rapid generation of precise molecular assemblies to investigate multivalent interactions.

• 出版日期2017-4