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[Ag59(2,5-DCBT)32]3-: A new cluster and a precursor for three well-known clusters

Abstract

We report the synthesis of a new silver cluster, [Ag59(2,5-DCBT)32]3- (I) (2,5-DCBT: 2,5-dichlorobenzenethiol), which acts as a precursor for the synthesis of three well-known silver clusters, [Ag44(2,4-DCBT/4-FTP)30]4- (II) (4-FTP: 4-fluorothiophenol and 2,4-DCBT: 2,4-dichlorobenzenethiol), [Ag25(2,4-DMBT)18]- (III) (2,4-DMBT: 2,4-dimethylbenzenethiol) and [Ag29(1,3-BDT)12(PPh3)4]3- (IV) (1,3-BDT: 1,3-benzenedithiol and PPh3: triphenylphosphine). This newly synthesized silver cluster, I, is characterized using UV-vis absorption studies, high resolution electrospray ionization mass spectrometry (ESI MS) and other analytical tools. The optical absorption spectrum shows distinct features which are completely different from the previously reported silver clusters. We perform the rapid transformations of I to other well-known clusters II, III and IV by reaction with different thiols. Time-dependent UV-vis and ESI MS measurements reveal that I dissociates into distinct thiolate entities in presence of thiols and the thiolates recombine to produce different clusters. The conversion mechanism is found to be quite different from the previous reports where it occurs through the initial formation of ligand exchanged products. Here, we also show the synthesis of a different cluster core, [Ag44(2,4-DCBT)30]4- (IIa) using 2,4-DCBT, a structural isomer of 2,5-DCBT under the same synthetic conditions used for I. This observation demonstrates the effect of isomeric thiols in controlling the size of silver clusters. The conversion of one cluster to several other clusters under ambient conditions and the effect of ligand structure in silver cluster synthesis give new insights into the cluster chemistry.

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Publication details

The article was received on 08 Mar 2017, accepted on 16 May 2017 and first published on 18 May 2017


Article type: Paper
DOI: 10.1039/C7NR01670K
Citation: Nanoscale, 2017, Accepted Manuscript
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    [Ag59(2,5-DCBT)32]3-: A new cluster and a precursor for three well-known clusters

    E. KHATUN, A. Ghosh, D. Ghosh, P. Chakraborty, A. Nag, B. Mondal, S. Chennu and T. Pradeep, Nanoscale, 2017, Accepted Manuscript , DOI: 10.1039/C7NR01670K

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