Experimental and theoretical evidence for unprecedented strong interactions of gold atoms with boron on boron/sulfur-doped carbon surfaces.

The 16e square-planar bis-thiolato-Au(iii) complexes [Au(1,2-dicarba--dodecarborane-1,2-dithiolato)][NBu] (Au-1) and [Au(4-methyl-1,2-benzenedithiolato)][NBu] (Au-2) have been synthesized and fully characterized. Au-1 and Au-2 were encapsulated in the symmetrical triblock copolymer poloxamer (Pluronic®) P123 containing blocks of poly(ethylene oxide) and poly(propylene oxide), giving micelles AuMs-1 and AuMs-2. High electron flux in scanning transmission electron microscopy (STEM) was used to generate single gold atoms and gold nanocrystals on B/S-doped graphitic surfaces, or S-doped amorphous carbon surfaces from AuMs-1 and AuMs-2, respectively. Electron energy loss spectroscopy (EELS) data suggested strong interactions of gold atoms/nanocrystals with boron in the B/S-doped graphitic matrix. Density-functional theory (DFT) calculations, also supported the experimental findings, pointing towards strong Au-B bonds, depending on the charge on the Au-(B-graphene) fragment and the presence of further defects in the graphene lattice.