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Covalently linked multimers of gold nanoclusters Au 102(p-MBA) 44 and Au ~250(p-MBA) n

Covalently linked multimers of gold nanoclusters Au 102(p-MBA) 44 and Au ~250(p-MBA) n

Tanja Lahtinen, Eero Hulkko, Karolina Sokołowska, Tiia-Riikka Tero, Ville Saarnio, Johan Lindgren, Mika Pettersson, Hannu Häkkinen, Lauri Lehtovaara

Nanoscale. 2016 Nov 10;8(44):18665-18674.

PMID: 27714130

Abstract:

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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP6954274	Biphenyl-4,4′-dithiol		6954-27-4	Price

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