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Toward a Janus Cluster: Regiospecific Decarboxylation of Ag44(4-MBA)30@Ag Nanoparticles

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    Toward a Janus Cluster: Regiospecific Decarboxylation of Ag44(4-MBA)30@Ag Nanoparticles
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    DST Unit of Nanoscience (DST UNS) & Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India
    *E-mail: [email protected]; Fax: 91-44-2257-0545/0509 (T.P.).
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2016, 120, 28, 15471–15479
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    https://doi.org/10.1021/acs.jpcc.6b04769
    Published July 5, 2016
    Copyright © 2016 American Chemical Society
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    Abstract

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    The ligand shell structure of the aspicule Ag44(4-MBA)30 (MBA: mercaptobenzoic acid, in the thiolate form) was modified in a precise, site-specific manner. Laser irradiation at 633 nm of a monolayer assembly of plasmonic Ag nanoparticles (NPs) covered with Ag44(4-MBA)30 clusters leads to decarboxylation of 4-MBA ligands forming thiophenolate (TP) ligands. While the molecular identity and integrity of aspicules post laser irradiation were confirmed by ESI MS, time-dependent SERS spectra and computational studies suggest that the phenomenon of decarboxylation is limited to the 4-MBA ligands facing the NP surface. This creates modified Ag44 clusters, with 4-MBA ligands on one side and TP ligands on the other, giving them a two-faced (Janus) ligand structure. The ligand distribution of such clusters gets equilibrated in solution. We show that such selective transformation can be used to create molecular patterns. Janus clusters may be important in chemistry at biphasic interfaces.

    Copyright © 2016 American Chemical Society

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.6b04769.

    • Details of computation, characterization of nanoparticles, UV/vis of Ag44 cluster, comparative Raman spectra, intensity vs exposure time plot, and Raman spectral data of control experiments with Ag@PVP and Au@citrate nanoparticles (PDF)

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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2016, 120, 28, 15471–15479
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.6b04769
    Published July 5, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

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