Covalently linked multimers of gold nanoclusters Au102(p-MBA)44 and Au∼250(p-MBA)n
Lahtinen, T., Hulkko, E., Sokołowska, K., Tero, T.-R., Saarnio, V., Lindgren, J., Pettersson, M., Häkkinen, H., & Lehtovaara, L. (2016). Covalently linked multimers of gold nanoclusters Au102(p-MBA)44 and Au∼250(p-MBA)n. Nanoscale, 8(44), 18665-18674. https://doi.org/10.1039/C6NR05267C
DisciplineFysikaalinen kemiaOrgaaninen kemiaNanoscience CenterPhysical ChemistryOrganic ChemistryNanoscience Center
© The Royal Society of Chemistry 2016. This is a final draft version of an article whose final and definitive form has been published by RSC. Published in this repository with the kind permission of the publisher.
We present the synthesis, separation, and characterization of covalently-bound multimers of para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au102(p-MBA)44 nanocluster with biphenyl-4,4′-dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BPDT molecules. The linking chemistry is not specific to Au102(p-MBA)44. The same approach yields multimers also for a larger monodisperse p-MBA-protected cluster of approximately 250 gold atoms, Au∼250(p-MBA)n. While the Au102(p-MBA)44 is not plasmonic, the Au∼250(p-MBA)n nanocluster supports localized surface plasmon resonance (LSPR) at 530 nm. Multimers of the Au∼250(p-MBA)n exhibit additional transitions in their UV-vis spectrum at 630 nm and 810 nm, indicating the presence of hybridized LSPR modes. Well-defined structures and relatively small sizes make these systems excellent candidates for connecting ab initio theoretical studies and experimental quantum plasmonics. Moreover, our work opens new possibilities in the controlled synthesis of advanced monodisperse nanocluster superstructures. ...
PublisherRoyal Society of Chemistry Publishing; National Center for Nanoscience and Technology
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Related funder(s)Academy of Finland
Funding program(s)Academy Project, AoF; Research post as Academy Research Fellow, AoF
Additional information about fundingThis work was financially supported by the Academy of Finland via projects 269402 and 273499 (L. L.), 265502 (E. H.), and 266492 (H. H.), the computations were made at the NSC and at CSC – the Finnish IT Center for Science in Espoo. We acknowledge Prof. T. Tsukuda, Assoc. Prof. K. Koyasu, an Mr K. Hirata for resources and support to measure the mass spectrum of Au102( p-MBA)44 in the University of Tokyo, during a visit (T.-R. T.) supported by the University of Jyväskylä. We acknowledge Drs A. Johansson, G. Groenhof, P. Papponen, and Ms E. Pohjolainen for technical help and Drs X. Chen, J. Koivisto, S. Malola, and K. Salorinne for fruitful discussions. ...
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