A1 Journal article (refereed)
Dithiol-Induced Oligomerization of Thiol-Protected Gold Nanoclusters (2018)

Sokolowska, K., Hulkko, E., Lehtovaara, L., & Lahtinen, T. (2018). Dithiol-Induced Oligomerization of Thiol-Protected Gold Nanoclusters. Journal of Physical Chemistry C, 122(23), 12524-12533. https://doi.org/10.1021/acs.jpcc.8b02988

JYU authors or editors

Hulkko, Eero
Lehtovaara, Lauri
Lahtinen, Tanja
Sokolowska, Karolina

Publication details

All authors or editors: Sokolowska, Karolina; Hulkko, Eero; Lehtovaara, Lauri; Lahtinen, Tanja

Journal or series: Journal of Physical Chemistry C

ISSN: 1932-7447

eISSN: 1932-7455

Publication year: 2018

Volume: 122

Issue number: 23

Pages range: 12524-12533

Publisher: American Chemical Society

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acs.jpcc.8b02988

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/59663

Abstract

Controlled synthesis of nanostructure oligomers requires detailed understanding of their wet chemistry and the forces driving the polymerization process. In this paper, we report the main factors affecting the reaction yields of a dithiol-induced synthesis of covalently bound nanocluster dimers and oligomers and present a detailed analysis of possible reaction mechanisms. We synthesize the nanocluster oligomers using monodisperse para-mercaptobenzoic acid (p-MBA)-protected gold nanoclusters with a nominal composition of Au∼250(p-MBA)n to minimize ensemble effects on size, shape, and surface structure. Ligand exchange was performed on the nanoclusters with five different dithiol linkers: 5,5′-bis(mercaptomethyl)-2,2′-bipyridine, 4,4″-thiobisbenzenethiol, benzene-1,4-dithiol, 1,4-benzenedimethanethiol, and dimercaptostilbene. Oligomer yields depend strongly on the used dithiol and on the dithiol-to-nanocluster ratio. Detailed analysis of the reaction yields in combination with simulations suggests that the system reaches a dynamic equilibrium, where ligand exchange happens continuously forming and breaking nanocluster oligomers that are bound together by short chains of disulfide-bridged dithiols. Despite the dynamic nature of the system, dithiol-induced polymerization of nanoclusters is a general and straightforward approach to produce dimers and larger oligomers of thiol-protected nanoclusters. Our work provides physical insight into, offers tools for, and reveals challenges in the controlled synthesis of covalently bound nanoparticle assemblies.

Keywords: nanoparticles; oligomer

Fields of science: