Fluorinated gold thiolate nanoparticles by Brust synthesis and ligand exchange

AEI 37

Amala Dass, amaldass@email.unc.edu and Royce W. Murray. Kenan Laboratories of Chemistry, University of North Carolina, University of North Carolina, Chapel Hill, NC 27599
Metal nanoparticles exhibit specific catalytic, electrochemical, photophysical properties depending on their size. Specifically the evolution of size dependent properties of gold nanoparticles has been of great interest. The choice of ligand plays a major role in the properties of nanoparticles. Fluorinated thiolate ligands may lead to interesting organization of nanoparticles due to their hydrophobic nature, low surface tension and immiscibility with common organic solvents(1,2,3 ) We have shown two routes to synthesize F-MPC's: 1) ligand exchange reaction with Au55(PPh3)Cl6 2) modified Brust synthesis using fluorinated thiols

Perfluorobenzene thiol was ligand exchanged with Au55(PPh3)Cl6 to yield fluorinated nanoparticles, Au75(SC6F5)32 with minimal PPh3 impurity. Electrochemical and optical behaviour of these polydisperse nanoparticles are quite similar to the Au75(SC6)40. Modified Brust synthesis(5) was done using 1H, 1H, 2H, 2H - perfluorodecanethiol. Fluorinated MPC's by this route are not soluble in common organic solvents like toluene and CH2Cl2 and are soluble in fluorinated solvents. MALDI-MS reveals a mixture of ~44 atoms and ~75 atoms species. UV-Vis spectra of these particles featureless decay characteristic of <2nm and polydisperse particles. Further supportive TGA, NMR, XPS data are presented(4).

This project has been supported by grants from the NSF.

References: 1. Barriet, D; Lee, T.R. Curr. Opin. Colloid Interface Sci. 2003, 8, 236-242. 2. Yonezawa, T; Onoue, S.; Kimizuka, N. Langmuir, 2001, 17, 2291-2293. 3. Esumi, K; Sarashina, S; Yoshimura, T; Langmuir, 2004, 20, 5189-5191. 4. Dass, A; Guo, R; Balasubramanian, R.; Tracy, J.; Douglas, A.; Murray, R. W; manuscript in preparation. 5. Price, R. C.; Whetten, R. L. J. Am. Chem. Soc., 2005, 127, 13750-13751.