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Direct versus Ligand-Exchange Synthesis of [PtAg28(BDT)12(TPP)4]4─ Nanoclusters: Effect of Single-Atom Dopant on the Optoelectronic and Chemical Properties

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 PtAg28 cluster, modulates its electronic structure and enhances its photoluminescence intensity and excited-state lifetime, and also enables solvent interactions with the NCs 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 to the exploration of novel multimetallic NCs.

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Publication details

The article was received on 21 Apr 2017, accepted on 31 May 2017 and first published on 07 Jun 2017


Article type: Paper
DOI: 10.1039/C7NR02844J
Citation: Nanoscale, 2017, Accepted Manuscript
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    Direct versus Ligand-Exchange Synthesis of [PtAg28(BDT)12(TPP)4]4─ Nanoclusters: Effect of Single-Atom Dopant on the Optoelectronic and Chemical Properties

    M. Bootharaju, S. Kozlov, Z. Cao, M. Harb, M. Parida, M. N. Hedhili, O. F. Mohammed, O. M. Bakr, L. Cavallo and J. Basset, Nanoscale, 2017, Accepted Manuscript , DOI: 10.1039/C7NR02844J

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