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Issue 16, 2018
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Nanocluster superstructures or nanoparticles? The self-consuming scaffold decides

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Abstract

We show that using the same reaction procedure, by hindering or allowing the formation of a reaction intermediate, the Ag+dodecanethiolate polymeric complex, it is possible to selectively obtain Ag dodecanethiolate nanoparticles or Ag dodecanethiolate nanoclusters in the size range 4–2 nm. Moreover, the Ag dodecanethiolate nanoclusters display a lamellar superstructure templated from the precursor Ag+dodecanethiolate polymeric complex. A plausible formation mechanism is illustrated where, starting from the precursor and scaffold lamellar Ag+ thiolate polymeric complex, first the nanocluster Agn0 core is formed by reduction of isoplanar Ag+ ions, followed by Ag+ thiolate units that build protection, the nanocluster shell, around the core. The nanoclusters are characterized by elemental analyses, XRD, ATR-FTIR, XPS, XAS, MALDI, ESI, UV-Vis and fluorescence measurements. The luminescent Ag15(dodecanethiolate)11·2H2O nanocluster is achieved in good yield after 4 hours of reaction whereas after 2 hours, the luminescent Ag35(dodecanethiolate)16 is isolated. Both Ag nanoclusters present emission bands in the range 330–450 nm, the shifting depending on the excitation wavelength. This phenomenon is attributed to a possible dipolar state causing distribution in energies due to variability of dipole–dipole interactions. Moreover, both nanoclusters further present a NIR emission at about 700 nm independent from the excitation wavelength. Thanks to their optical and structural properties, the synthesized nanoclusters, perfect molecular/nanoparticle hybrids, have great potentiality for new applications in nanotechnologies.

Graphical abstract: Nanocluster superstructures or nanoparticles? The self-consuming scaffold decides

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Publication details

The article was received on 21 Dec 2017, accepted on 20 Mar 2018 and first published on 20 Mar 2018


Article type: Paper
DOI: 10.1039/C7NR09520A
Citation: Nanoscale, 2018,10, 7472-7483
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    Nanocluster superstructures or nanoparticles? The self-consuming scaffold decides

    L. Suber, P. Imperatori, L. Pilloni, D. Caschera, N. Angelini, A. Mezzi, S. Kaciulis, A. Iadecola, B. Joseph and G. Campi, Nanoscale, 2018, 10, 7472
    DOI: 10.1039/C7NR09520A

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