@article {163, title = {Macropolyhedral syn-B18H22, the {\textquotedblleft}Forgotten{\textquotedblright} Isomer}, journal = {Journal of the American Chemical Society}, volume = {145}, year = {2023}, month = {August 2, 2023}, pages = {17975-17986}, chapter = {17975}, abstract = {

The chemistry and physics of macropolyhedral B18H22 clusters have attracted significant attention due to the interesting photophysical properties of anti-B18H22 (blue emission, laser properties) and related potential applications. We have focused our attention on the {\textquotedblleft}forgotten{\textquotedblright} syn-B18H22 isomer, which has received very little attention since its discovery compared to its anti-B18H22 isomer, presumably because numerous studies have reported this isomer as nonluminescent. In our study, we show that in crystalline form, syn-B18H22 exhibits blue fluorescence and becomes phosphorescent when substituted at various positions on the cluster, associated with peculiar microstructural-dependent effects. This work is a combined theoretical and experimental investigation that includes the synthesis, separation, structural characterization, and first elucidation of the photophysical properties of three different monothiol-substituted cluster isomers, [1-HS-syn-B18H21] 1, [3-HS-syn-B18H21] 3, and [4-HS-syn-B18H21] 4, of which isomers 1 and 4 have been proved to exist in two different polymorphic forms. All of these newly substituted macropolyhedral cluster derivatives (1, 3, and 4) have been fully characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, IR spectroscopy, and luminescence spectroscopy. This study also presents the first report on the mechanochromic shift in the luminescence of a borane cluster and generally enriches the area of rather rare boron-based luminescent materials. In addition, we present the first results proving that they are useful constituents of carbon-free self-assembled monolayers.

}, keywords = {boron, boron hydride, Cluster, luminescence, macropolyhedral, NMR, PXRD, SAM, self-assembly, single crystal, solid state, syn-B18H22, XPS}, doi = {https://doi.org/10.1021/jacs.3c05530}, url = {https://pubs.acs.org/doi/10.1021/jacs.3c05530}, author = {Deepak Kumar Patel and B. S. Sooraj and Kaplan Kirakci and Jan Machacek and Monika Kucerakova and Jonathan Bould and Michal Dusek and Martha Frey and Christof Neumann and Sundargopal Ghosh and Andrey Turchanin and Thalappil Pradeep and Tomas Base} } @article {119, title = {Decaborane Thiols as Building Blocks for Self-Assembled Monolayers on Metal Surfaces}, journal = {Inorganic Chemistry}, volume = {51}, year = {2012}, chapter = {1685}, abstract = {

Three nido-decaborane thiol cluster compounds, [1-(HS)-nido-B10H13] 1, [2-(HS)-nido-B10H13] 2, and [1,2-(HS)2-nido-B10H12] 3 have been characterized using NMR spectroscopy, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. In the solid state, 1, 2, and 3 feature weak intermolecular hydrogen bonding between the sulfur atom and the relatively positive bridging hydrogen atoms on the open face of an adjacent cluster. Density functional theory (DFT) calculations show that the value of the interaction energy is approximately proportional to the number of hydrogen atoms involved in the interaction and that these values are consistent with a related bridging-hydrogen atom interaction calculated for a B18H22 C6H6 solvate. Self-assembled monolayers (SAMs) of 1, 2, and 3 on gold and silver surfaces have been prepared and characterized using X-ray photoelectron spectroscopy. The variations in the measured sulfur binding energies, as thiolates on the surface, correlate with the (CC2) calculated atomic charge for the relevant boron vertices and for the associated sulfur substituents for the parent B10H13(SH) compounds. The calculated charges also correlate with the measured and DFT-calculated thiol 1H chemical shifts. Wetting-angle measurements indicate that the hydrophilic open face of the cluster is directed upward from the substrate surface, allowing the bridging hydrogen atoms to exhibit a similar reactivity to that of the bulk compound. Thus, [PtMe2(PMe2Ph)2] reacts with the exposed and acidic B }, doi = {10.1021/ic202000b}, author = {Jonathan Bould and Jan Machacek and Michael G S Londesborough and Ramon Macias and John D Kennedy and Zdenek Bastl and Patrik Rupper and Tomas Base} } @article {123, title = {Reversible Capture of Small Molecules On Bimetallaborane Clusters: Synthesis, Structural Characterization, and Photophysical Aspects}, journal = {Inorganic Chemistry}, volume = {50}, year = {2011}, chapter = {7511}, doi = {10.1021/ic200374k}, url = {http://pubs.acs.org/doi/abs/10.1021\%2Fic200374k}, author = {Jonathan Bould and Tomas Base and Michael G S Londesborough and Luis A Oro and Ramon Macias and John D Kennedy and Pavel Kubat and Marcel Fuciman and Tomas Polivka and Kamil Lang} } @article {117, title = {Carborane-thiol-silver interactions. A comparative study of the molecular protection of silver surfaces}, journal = {Surface and Coatings Technology}, volume = {204}, year = {2010}, chapter = {2639}, abstract = {

The interaction between flat silver surfaces and carboranethiol derivatives, and its relevance regarding the molecular protection of silver against corrosion by hydrogen sulphide, are reported here. A comparison of the protective qualities of four carboranethiols (1-HS-1,2-C2B10H11, 1,2-(HS)2-1,2-C2B10H10, 9,12-(HS)2-1,2-C2B10H10, and 1,12-(HS)2-1,2-C2B10H10) with several organic thiols (1-butanethiol, 1-octanethiol, 1-dodecanethiol, benzene-1,2-dithiol, benzenethiol, and sodium 2-mercaptoethanesulphonate) is provided. All these derivatives are categorized according to their capacity to inhibit the interaction of silver with H2S in the presence of water molecules in the gas phase. We found that significantly better molecular protection for silver surfaces is afforded by the carboranethiol derivatives, and, of these, 9,12-(HS)2-1,2-C2B10H10 proved to be particularly effective. The corrosion of silver by H2S is accompanied by well-defined colour changes from lustrous silver, through yellow, violet, blue, and finally to grey. This sequence has not been reported before and it is used in this study as a qualitative indicator of the extent of silver corrosion. Our results are supported by reflectance UV

}, doi = {10.1016/j.surfcoat.2010.02.019}, url = {http://www.sciencedirect.com/science/article/pii/S0257897210001106}, author = {Tomas Base and Zdenek Bastl and Vladimir Havranek and Kamil Lang and Jonathan Bould and Michael G S Londesborough and Jan Machacek and Jaromir Plesek} } @article {124, title = {An Experimental Solution to the "Missing Hydrogens" Question Surrounding the Macropolyhedral 19-Vertex Boron Hydride Monoanion [B19H22](-), a Simplification of Its Synthesis, and Its Use As an Intermediate in the First Example of syn-B18H22 to anti-B18H22}, journal = {Inorganic Chemistry}, volume = {49}, year = {2010}, chapter = {4092}, doi = {10.1021/IC901976y}, url = {http://pubs.acs.org/doi/abs/10.1021/ic901976y}, author = {Michael G S Londesborough and Jonathan Bould and Tomas Base and Drahomir Hnyk and Mario Bakardjiev and Josef Holub and Ivana Cisarova and John D Kennedy} }