Abstract
In single crystals of 2-naphthylisonitrile-gold(i)-halide (halide = Cl, Br, I) complexes, AuAu distances are found to be significantly shorter than twice the van der Waals radius, indicating attractive interactions between gold atoms in adjacent molecules. In the particular case of the studied 2-naphthylisonitrile-gold(i) complexes, homodimers are the common structural motifs, in which the linearly coordinated gold exhibits a crossed swords arrangement with the Au atoms of two molecules being at the intersection point. The crossed swords motif is preserved upon physical vapour deposition of both the chlorine and bromine derivatives on amorphous substrates like glass and glassy carbon. The determined activation energies of desorption for the chlorine (0.9 eV) and the bromine (1.2 eV) derivative are comparable to that of unsubstituted naphthalene. Using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ion scattering (RBS), we confirmed the chemical integrity of the molecules in thin films and revealed the orientation of the crossed swords dimers with respect to the substrate surface.
Highlights
Besides electrochemical procedures, physical and chemical vapour deposition (PVD and CVD) techniques are frequently used in science and technology for gold-plating and the preparation of thin gold films or small structures.[1,2] Such techniques play a crucial role in the field of microelectronics, but may be important for sensing applications or heterogeneous gold catalysis.[3]
The activation energy for evaporation of (NapNC)AuCl and (NapNC)AuBr is slightly higher than the value for unsubstituted naphthalene indicating that the ππ stacking of the naphthyl groups dominates the structure formation of the obtained bulk structures
In contrast to the chlorido and bromido derivatives, we were not able to grow films by physical vapour deposition for the iodido derivative, which apparently decomposes upon heating instead of subliming
Summary
Physical and chemical vapour deposition (PVD and CVD) techniques are frequently used in science and technology for gold-plating and the preparation of thin gold films or small structures.[1,2] Such techniques play a crucial role in the field of microelectronics, but may be important for sensing applications or heterogeneous gold catalysis.[3]. The storage of gold-containing solutions for some hours or days at room temperature leads to a violet precipitate of colloidal gold This behaviour can be traced back to the intrinsic thermal instability of many gold complexes due to the high oxidation potential of gold(I) and the general tendency to form elemental gold. Heavy elements with closed shell configurations (d8, d10, and s2) are capable of forming such so-called metallophilic interactions.[18,19] For gold(I) atoms these interactions are strong This is the reason why the interaction between gold(I) atoms is referred to as aurophilicity.[20,21,22,23] First evidence of gold atoms attracting each other was found in the 1970s.
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