title: Intercluster Reactions between Au25(SR)18 and Ag44(SR)30.
abstract: We present the first example of intercluster reactions between atomically precise, monolayer protected noble metal clusters using Au25(SR)18 and Ag44(SR)30 (RS- = alkyl/aryl thiolate) as model compounds. These clusters undergo spontaneous reaction in solution at ambient conditions. Mass spectrometric measurements both by electrospray ionization and matrix assisted laser desorption ionization show that the reaction occurs through the exchange of metal atoms and protecting ligands of the clusters. Intercluster alloying is demonstrated to be a much more facile method for heteroatom doping into Au25(SR)18, as observed by doping up to 20 Ag atoms. We investigated the thermodynamic feasibility of the reaction using DFT calculations and a tentative mechanism has been presented. Metal core-thiolate interfaces in these clusters play a crucial role in inducing these reactions and also affect rates of these reactions. We hope that our work will help accelerate activities in this area to establish chemistry of monolayer protected clusters.
authors.affiliation: DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras , Chennai, 600 036, India.
authors.forename: K R
authors.initials: KR
authors.lastname: Krishnadas
authors.affiliation: DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras , Chennai, 600 036, India.
authors.forename: Atanu
authors.initials: A
authors.lastname: Ghosh
authors.affiliation: DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras , Chennai, 600 036, India.
authors.forename: Ananya
authors.initials: A
authors.lastname: Baksi
authors.affiliation: DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras , Chennai, 600 036, India.
authors.forename: Indranath
authors.initials: I
authors.lastname: Chakraborty
authors.affiliation: DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras , Chennai, 600 036, India.
authors.forename: Ganapati
authors.initials: G
authors.lastname: Natarajan
authors.affiliation: DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras , Chennai, 600 036, India.
authors.forename: Thalappil
authors.initials: T
authors.lastname: Pradeep