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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

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
M.S. Bootharaju, S.M. Kozlov, Z. Cao, M. Harb, M.R. Parida, M.N. Hedhili, O.F. Mohammed, O.M. Bakr, L. Cavallo, J.-M. Basset
Nanoscale, 9, 9529-9536 , (2017)​
M.S. Bootharaju, S.M. Kozlov, Z. Cao, M. Harb, M.R. Parida, M.N. Hedhili, O.F. Mohammed, O.M. Bakr, L. Cavallo, J.-M. Basset
Nanocluster, Optoelectronics
2017



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 PtAg28NCs 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 PtAg28could not be replaced by Au, unlike the central Ag of Ag29 NCs. The achieved synthesis of single-sized PtAg28clusters will facilitate further applications of the LE strategy for the exploration of novel multimetallic NCs.​
DOI: 10.1039/C7NR02844J