Permethylated 12-Vertex p-Carborane Self-Assembled Monolayers

• Published in: Journal of physical chemistry. C Vol. 115; no. 46; pp. 22998 - 23007
• Main Authors: Scholz, Frank, Nothofer, Heinz-Georg, Wessels, Jurina M, Nelles, Gabriele, von Wrochem, Florian, Roy, Subhadeep, Chen, Xudong, Michl, Josef
• Format: Journal Article
• Language: English
• Published: American Chemical Society 24.11.2011
• Subjects: C: Surfaces, Interfaces, Catalysis
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/jp207133a

closo-Carborane cages and their adsorption onto metal surfaces is a subject of growing interest because of the distinct structural and electronic properties of boron carbide derivatives. Nevertheless, the extent to which the substitution of the cage alters structural and spectroscopic characteristics of closo-carborane monolayers has not been investigated so far. In this paper, core level shifts and valence electronic structure of two different p-carboranes, the parent and the (2,11)-decamethylated 12-vertex closo-1,12-dicarbadodecaborane, are compared using photoemission spectroscopy, whereas the lateral arrangement of the molecules on gold is investigated by scanning tunneling microscopy. Both compounds present a significant energy gap between the molecular highest occupied molecular orbital (HOMO) and the Fermi level of Au (∼4 eV), attributed to the high ionization potential of boron carbides. Permethylation of the p-carborane cage induces a charge redistribution resulting in a shift of the boron 1s core level signal (Δ E = 0.25 eV) and in a change of the molecular dipole moment; the HOMO level is concomitantly shifted by ∼0.5 eV to lower binding energies. The dense molecular packing (intermolecular distance of 7 Å for closo-1,12-dicarbadodecaborane and 10 Å for its permethylated counterpart) is defined by the physical diameter of the carborane cage and by intermolecular dispersion forces. For both carboranes, the overlayer structure shows incommensurism with the Au(111) substrate, but due to the higher intermolecular forces acting between the parent closo-1,12-dicarbadodecaboranes a polycrystalline phase is observed with a significantly higher coherence length than for the permethylated analogue.