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

Handle URI:
http://hdl.handle.net/10754/625415
Title:
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
Authors:
Bootharaju, Megalamane Siddaramappa ( 0000-0002-8276-6987 ) ; Kozlov, Sergey M.; Cao, Zhen; Harb, Moussab ( 0000-0001-5540-9792 ) ; Parida, Manas R.; Hedhili, Mohamed N. ( 0000-0002-3624-036X ) ; Mohammed, Omar F. ( 0000-0001-8500-1130 ) ; Bakr, Osman M. ( 0000-0002-3428-1002 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
Heteroatom 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.
KAUST Department:
KAUST Catalysis Center (KCC); KAUST Solar Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia; Imaging and Characterization Core Lab
Citation:
Bootharaju 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.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Nanoscale
KAUST Grant Number:
k1133; k1211
Issue Date:
7-Jun-2017
DOI:
10.1039/c7nr02844j
Type:
Article
ISSN:
2040-3364; 2040-3372
Sponsors:
We 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.
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2017/NR/C7NR02844J#!divAbstract
Appears in Collections:
Articles; Advanced Nanofabrication, Imaging and Characterization Core Lab; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBootharaju, Megalamane Siddaramappaen
dc.contributor.authorKozlov, Sergey M.en
dc.contributor.authorCao, Zhenen
dc.contributor.authorHarb, Moussaben
dc.contributor.authorParida, Manas R.en
dc.contributor.authorHedhili, Mohamed N.en
dc.contributor.authorMohammed, Omar F.en
dc.contributor.authorBakr, Osman M.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2017-08-29T12:47:48Z-
dc.date.available2017-08-29T12:47:48Z-
dc.date.issued2017-06-07en
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.en
dc.identifier.issn2040-3364en
dc.identifier.issn2040-3372en
dc.identifier.doi10.1039/c7nr02844jen
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.en
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.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2017/NR/C7NR02844J#!divAbstracten
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 propertiesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentKAUST Solar Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabiaen
dc.contributor.departmentImaging and Characterization Core Laben
dc.identifier.journalNanoscaleen
kaust.authorBootharaju, Megalamane Siddaramappaen
kaust.authorKozlov, Sergey M.en
kaust.authorCao, Zhenen
kaust.authorHarb, Moussaben
kaust.authorParida, Manas R.en
kaust.authorHedhili, Mohamed N.en
kaust.authorMohammed, Omar F.en
kaust.authorBakr, Osman M.en
kaust.authorCavallo, Luigien
kaust.authorBasset, Jean-Marieen
kaust.grant.numberk1133en
kaust.grant.numberk1211en
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