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
Kozlov, Sergey M.
Parida, Manas R.
Hedhili, Mohamed N.
Mohammed, Omar F.
KAUST DepartmentKAUST Catalysis Center (KCC)
KAUST Solar Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
Imaging and Characterization Core Lab
KAUST Grant Numberk1133
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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)
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