Reversible Site-Selective Editing of Atomically Precise Au6 Nanoclusters through Controlled Oxidative Addition/Reductive Elimination
Year: 2026
Type: preprint
Abstract: Enacting precise bond formations and dissociations at specific sites is focal to molecular editing of functional materials but remains difficult to achieve on the surfaces of metal nanoparticles. Here, we demonstrate the first site-selective molecular editing of a multidentate ligand-stabilized [Au6(SbP3)2][PF6]2 (Au6) nanocluster (where, SbP3= tris(2-(diphenylphosphino)phenyl)stibine), using iodobenzene dichloride (PhICl2). Treatment of the parent Au6 cluster with PhICl2 leads to selective oxidative chlorination across one Au-Au bond, affording a new [Au6(SbP3)2Cl2][PF6]2 (Au6Cl2) nanocluster. Single-crystal X-ray diffraction of Au6Cl2 reveals a rearrangement of the parent Au6 core, with complete detachment of one gold atom from the core. Further, Au6Cl2 crystallizes as a racemic mixture, in contrast to the achiral parent cluster. The electronic structure and optical properties of the Au6Cl2 nanocluster was analyzed experimentally and theoretically, depicting good correlation. The Au6 to Au6Cl2 transformation is readily monitored by UV-visible absorption, NMR spectroscopy, and electrospray ionization mass spectrometry (ESI-MS). Remarkably, treatment of Au6Cl2 with sodium borohydride (NaBH4) regenerates the original Au6 cluster, establishing a reversible cluster transformation reaction. Taken together, this work illustrates how commonly used oxidizing and reducing reagents can be used to achieve site-specific, reversible structural editing of metal nanoclusters, providing a general strategy for tailoring their structural, optical, and chiroptical properties.
Source: ChemRxiv
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
Awards: Prairie Light: Next Generation Networking for Mid-continent Science, Collaborative Research: Structural Control of Energy Transfer in Atomically Precise Nanoclusters, Single Crystal X-ray Diffractometer with Microfocus Rotating Anode Source (Cu), LEAPS-MPS: Heterogeneous Asymmetric Catalysis with Chiral Metal Clusters, Collaborative Research: EPSCoR RII Track 2 Oklahoma and Kansas: A cyberCommons for Ecological Forecasting, MRI: Acquisition of a GPU-Enabled Computer Cluster for Molecular Modeling Applications
OpenAlex ID: W7208749316