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    Switching a Nanocluster Core from Hollow to Non-hollow

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    Type
    Article
    Authors
    Bootharaju, Megalamane Siddaramappa cc
    Joshi, Chakra Prasad
    Alhilaly, Mohammad Jaber cc
    Bakr, Osman cc
    KAUST Department
    Functional Nanomaterials Lab (FuNL)
    KAUST Catalysis Center (KCC)
    KAUST Solar Center (KSC)
    Material Science and Engineering Program
    Physical Science and Engineering (PSE) Division
    Date
    2016-04-12
    Online Publication Date
    2016-04-12
    Print Publication Date
    2016-05-24
    Permanent link to this record
    http://hdl.handle.net/10754/603946
    
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    Abstract
    Modulating the structure-property relationship in atomically precise nanoclusters (NCs) is vital for developing novel NC materials and advancing their applications. While promising biphasic ligand-exchange (LE) strategies have been developed primarily to attain novel NCs, understanding the mechanistic aspects involved in tuning the core and the ligand-shell of NCs in such biphasic processes is challenging. Here, we design a single phase LE process that enabled us to elucidate the mechanism of how a hollow NC (e.g., [Ag44(SR)30]4-, -SR: thiolate) converts into a non-hollow NC (e.g., [Ag25(SR)18]-), and vice versa. Our study reveals that the complete LE of the hollow [Ag44(SPhF)30]4- NCs (–SPhF: 4-fluorobenzenethiolate) with incoming 2,4-dimethylbenzenethiol (HSPhMe2) induced distortions in the Ag44 structure forming the non-hollow [Ag25(SPhMe2)18]- by a disproportionation mechanism. While the reverse reaction of [Ag25(SPhMe2)18]- with HSPhF prompted an unusual dimerization of Ag25, followed by a rearrangement step that reproduces the original [Ag44(SPhF)30]4-. Remarkably, both the forward and the backward reactions proceed through similar size intermediates that seem to be governed by the boundary conditions set by the thermodynamic and electronic stability of the hollow and non-hollow metal cores. Furthermore, the resizing of NCs highlights the surprisingly long-range effect of the ligands which are felt by atoms far deep in the metal core, thus opening a new path for controlling the structural evolution of nanoparticles.
    Citation
    Switching a Nanocluster Core from Hollow to Non-hollow 2016 Chemistry of Materials
    Sponsors
    Financial support for this work was provided by KAUST.
    Publisher
    American Chemical Society (ACS)
    Journal
    Chemistry of Materials
    DOI
    10.1021/acs.chemmater.5b05008
    Additional Links
    http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b05008
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.chemmater.5b05008
    Scopus Count
    Collections
    Material Science and Engineering Program; KAUST Solar Center (KSC); KAUST Catalysis Center (KCC); Physical Science and Engineering (PSE) Division; Articles

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