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dc.contributor.authorBootharaju, Megalamane Siddaramappa
dc.contributor.authorKozlov, Sergey
dc.contributor.authorCao, Zhen
dc.contributor.authorHarb, Moussab
dc.contributor.authorParida, Manas R.
dc.contributor.authorHedhili, Mohamed N.
dc.contributor.authorMohammed, Omar F.
dc.contributor.authorBakr, Osman
dc.contributor.authorCavallo, Luigi
dc.contributor.authorBasset, Jean-Marie
dc.date.accessioned2017-08-29T12:47:48Z
dc.date.available2017-08-29T12:47:48Z
dc.date.issued2017
dc.identifier.citationBootharaju MS, Kozlov SM, Cao Z, Harb M, Parida MR, et al. (2017) Direct versus ligand-exchange synthesis of [PtAg28(BDT)12(TPP)4]4− nanoclusters: effect of a single-atom dopant on the optoelectronic and chemical properties. Nanoscale 9: 9529–9536. Available: http://dx.doi.org/10.1039/c7nr02844j.
dc.identifier.issn2040-3364
dc.identifier.issn2040-3372
dc.identifier.pmid28660944
dc.identifier.doi10.1039/c7nr02844j
dc.identifier.urihttp://hdl.handle.net/10754/625415
dc.description.abstractHeteroatom doping of atomically precise nanoclusters (NCs) often yields a mixture of doped and undoped products of single-atom difference, whose separation is extremely difficult. To overcome this challenge, novel synthesis methods are required to offer monodisperse doped NCs. For instance, the direct synthesis of PtAg28 NCs produces a mixture of [Ag29(BDT)12(TPP)4]3- and [PtAg28(BDT)12(TPP)4]4- NCs (TPP: triphenylphosphine; BDT: 1,3-benzenedithiolate). Here, we designed a ligand-exchange (LE) strategy to synthesize single-sized, Pt-doped, superatomic Ag NCs [PtAg28(BDT)12(TPP)4]4- by LE of [Pt2Ag23Cl7(TPP)10] NCs with BDTH2 (1,3-benzenedithiol). The doped NCs were thoroughly characterized by optical and photoelectron spectroscopy, mass spectrometry, total electron count, and time-dependent density functional theory (TDDFT). We show that the Pt dopant occupies the center of the PtAg28 cluster, modulates its electronic structure and enhances its photoluminescence intensity and excited-state lifetime, and also enables solvent interactions with the NC surface. Furthermore, doped NCs showed unique reactivity with metal ions - the central Pt atom of PtAg28 could not be replaced by Au, unlike the central Ag of Ag29 NCs. The achieved synthesis of single-sized PtAg28 clusters will facilitate further applications of the LE strategy for the exploration of novel multimetallic NCs.
dc.description.sponsorshipWe gratefully acknowledge the use of core-lab facilities of KAUST. The calculations were performed on the Shaheen II supercomputer under the projects k1133 and k1211.
dc.publisherRoyal Society of Chemistry (RSC)
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2017/NR/C7NR02844J#!divAbstract
dc.titleDirect versus ligand-exchange synthesis of [PtAg28(BDT)12(TPP)4]4− nanoclusters: effect of a single-atom dopant on the optoelectronic and chemical properties
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentFunctional Nanomaterials Lab (FuNL)
dc.contributor.departmentImaging and Characterization Core Lab
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentKAUST Solar Center (KSC)
dc.contributor.departmentMaterial Science and Engineering Program
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.contributor.departmentSurface Science
dc.contributor.departmentUltrafast Laser Spectroscopy and Four-dimensional Electron Imaging Research Group
dc.identifier.journalNanoscale
kaust.personBootharaju, Megalamane Siddaramappa
kaust.personKozlov, Sergey
kaust.personCao, Zhen
kaust.personHarb, Moussab
kaust.personParida, Manas R.
kaust.personHedhili, Mohamed N.
kaust.personMohammed, Omar F.
kaust.personBakr, Osman M.
kaust.personCavallo, Luigi
kaust.personBasset, Jean-Marie
kaust.grant.numberk1133
kaust.grant.numberk1211


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