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
AuthorsBootharaju, Megalamane Siddaramappa
Parida, Manas R.
Hedhili, Mohamed N.
Mohammed, Omar F.
KAUST DepartmentChemical Science Program
Functional Nanomaterials Lab (FuNL)
Imaging and Characterization Core Lab
KAUST Catalysis Center (KCC)
KAUST Solar Center (KSC)
Material Science and Engineering Program
Physical Science and Engineering (PSE) Division
Ultrafast Laser Spectroscopy and Four-dimensional Electron Imaging Research Group
Permanent link to this recordhttp://hdl.handle.net/10754/625415
MetadataShow full item record
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.
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.
SponsorsWe 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.
PublisherRoyal Society of Chemistry (RSC)
- Stability, electronic structure, and optical properties of protected gold-doped silver Ag<sub>29-x</sub>Au<sub>x</sub> (x = 0-5) nanoclusters.
- Authors: Juarez-Mosqueda R, Malola S, Häkkinen H
- Issue date: 2017 May 31
- Gold Doping of Silver Nanoclusters: A 26-Fold Enhancement in the Luminescence Quantum Yield.
- Authors: Soldan G, Aljuhani MA, Bootharaju MS, AbdulHalim LG, Parida MR, Emwas AH, Mohammed OF, Bakr OM
- Issue date: 2016 May 4
- Distinct metal-exchange pathways of doped Ag25 nanoclusters.
- Authors: Bootharaju MS, Sinatra L, Bakr OM
- Issue date: 2016 Oct 6
- Observation of a new type of aggregation-induced emission in nanoclusters.
- Authors: Kang X, Wang S, Zhu M
- Issue date: 2018 Mar 21
- Unusual reactivity of dithiol protected clusters in comparison to monothiol protected clusters: studies using Ag<sub>51</sub>(BDT)<sub>19</sub>(TPP)<sub>3</sub> and Ag<sub>29</sub>(BDT)<sub>12</sub>(TPP)<sub>4</sub>.
- Authors: Ghosh A, Ghosh D, Khatun E, Chakraborty P, Pradeep T
- Issue date: 2017 Jan 19