@article {138, title = {The gaseous structure of closo-9,12-(SH)2-1,2-C2B10H10, a modifier of gold surfaces, as determined using electron diffraction and computational methods}, journal = {Dalton Transactions}, volume = {42}, year = {2013}, chapter = {12015}, abstract = {

The molecular structure of closo-9,12-(SH)2-1,2-C2B10H10 has been determined by the concerted use of quantum chemical calculations and gas electron diffraction (GED). For the purposes of GED, the architecture of the carbaborane cage was simplified to allow it to have C2v symmetry, while the positioning of the thiol groups means that the molecule had overall C1 symmetry. The accuracy of the experimental structure, as well as that calculated at the MP2(full)/6-311++G(3df,3pd) level, has been gauged by comparison of experimental 11B NMR chemical shifts with those calculated using gauge-invariant atomic orbitals (GIAO) methods. The inclusion of electron correlation in the magnetic property calculations (GIAO-MP2) gave superior results to those carried out using GIAO-HF. The electronic structure of this derivative, with respect to its directional interaction with a metal surface, is outlined.

}, doi = {10.1039/c3dt51393a}, url = {http://pubs.rsc.org/en/results?artrefjournalname=dalton\%20trans.\&artrefstartpage=12015\&artrefvolumeyear=2013\&fcategory=journal}, author = {Derek A Wann and Paul D Lane and Heather E Robertson and Tomas Base and Drahomir Hnyk} } @article {116, title = {Gold Micrometer Crystals Modified with Carboranethiol Derivatives}, journal = {J. Phys. Chem. C}, volume = {112}, year = {2008}, chapter = {14446}, abstract = {

The preparation and characterization of micrometer gold and silver single-crystals of well-defined shapes are reported here. The shapes of the crystals can be described as plates, polyhedra, and wires. The orientation of the crystal faces was studied using electron and X-ray powder diffraction techniques, and a (111) orientation of the large faces of gold plates was experimentally shown. The surface morphology of the crystal faces was studied by atomic force microscopy. Modifications of gold microplates with the thiolated carborane clusters 1,2-(HS)2-1,2-C2B10H10 (1), 9,12-(HS)2-1,2-C2B10H10 (2), and 1,12-(HS)2-1,12-C2B10H10 (3) are described. The carboranethiol molecules 1 and 2 show dipole moments of 4.1 and 5.9 D. In comparison, the thiolate derivative of compound 1 has a dipole moment of 4.7 D in the opposite direction to 1, and the thiolate form of compound 2 has a dipole moment of 16.7 D in the same direction. On the basis of X-ray photoelectron spectroscopy (XPS) analyses and values of work functions, we revealed that the molecules of 1 and 2 attached to the gold surface have similar electron distribution and dipole moments as within the free thiol derivatives. Following the modification of microplate gold crystals with 3, a monolayer of gold nanoparticles was attached on top of the carborane moieties. The composition of the surface species was studied using XPS. Dynamic contact angles of water on the modified gold surfaces are also discussed.

}, doi = {10.1021/jp802281s}, url = {http://pubs.acs.org/doi/abs/10.1021/jp802281s}, author = {Tomas Base and Zdenek Bastl and Miroslav Slouf and Mariana Klementova and Jan Subrt and Aliaksei Vetushka and Martin Ledinsky and Antonin Fejfar and Jan Machacek and Michael J Carr and Michael G S Londesborough} }