Switching a Nanocluster Core from Hollow to Non-hollow

Handle URI:
http://hdl.handle.net/10754/603946
Title:
Switching a Nanocluster Core from Hollow to Non-hollow
Authors:
Bootharaju, Megalamane Siddaramappa ( 0000-0002-8276-6987 ) ; Joshi, Chakra Prasad; Alhilaly, Mohammad J.; Bakr, Osman M. ( 0000-0002-3428-1002 )
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.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC)
Citation:
Switching a Nanocluster Core from Hollow to Non-hollow 2016 Chemistry of Materials
Publisher:
American Chemical Society (ACS)
Journal:
Chemistry of Materials
Issue Date:
24-Mar-2016
DOI:
10.1021/acs.chemmater.5b05008
Type:
Article
ISSN:
0897-4756; 1520-5002
Sponsors:
Financial support for this work was provided by KAUST.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b05008
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBootharaju, Megalamane Siddaramappaen
dc.contributor.authorJoshi, Chakra Prasaden
dc.contributor.authorAlhilaly, Mohammad J.en
dc.contributor.authorBakr, Osman M.en
dc.date.accessioned2016-03-30T07:31:17Zen
dc.date.available2016-03-30T07:31:17Zen
dc.date.issued2016-03-24en
dc.identifier.citationSwitching a Nanocluster Core from Hollow to Non-hollow 2016 Chemistry of Materialsen
dc.identifier.issn0897-4756en
dc.identifier.issn1520-5002en
dc.identifier.doi10.1021/acs.chemmater.5b05008en
dc.identifier.urihttp://hdl.handle.net/10754/603946en
dc.description.abstractModulating 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.en
dc.description.sponsorshipFinancial support for this work was provided by KAUST.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b05008en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b05008.en
dc.titleSwitching a Nanocluster Core from Hollow to Non-hollowen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalChemistry of Materialsen
dc.eprint.versionPost-printen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorBootharaju, Megalamane Siddaramappaen
kaust.authorJoshi, Chakra Prasaden
kaust.authorAlhilaly, Mohammad J.en
kaust.authorBakr, Osman M.en
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