Synthetically tailoring diamondoids for semiconductor applications
Final Report Abstract
The aim of this project was the target-oriented synthesis of new and known functionalized diamondoids (hydrogen-terminated nanodiamonds) and diamondoid cluster structures for the subsequent physical characterization and theoretical examination through the project partners within the Research Unit. We were able to synthesize the first ethylene bridged di- and tri-diamondoids and related hydrocarbons (primarily trishomocubanes for comparison) in sizable amounts (100–200 mg). The chemical and physical properties of these new compounds were examined in detail. We were also able to prepare thiolated diamondoids and, for the first time, their thiono-derivatives (thioketones); the latter were examined with respect to the theoretical prediction that they should be highly luminescent. This was shown to be true from the physical measurements. Finally, we prepared a large array of unsaturated diamondoids, in particular, an exciting adamantane pyrenophane that constitutes a model compound combining the carbon allotropes graphene and diamond in one molecule. Indeed, the combination of an electron emitter (adamantane) and an electron acceptor (pyrenophane) in combination with a highly bent aromatic system leads to a hydrocarbon with an unexpectedly large dipole moment. Determination of this dipole moment and the characterization of this new species as a rectifier component is currently ongoing. This work has been highlighted in ChemistryViews.
Publications
- Exploring covalently bound diamondoid particles with valence photoelectron spectroscopy. J. Chem. Phys. 139, 084310-084316, 2013
T. Zimmermann, R. Richter, A. Knecht, A.A. Fokin, T.V. Koso, L. V. Chernish, P. A. Gunchenko, P.R. Schreiner, T. Möller, and T. Rander
(See online at https://doi.org/10.1063/1.4818994) - UV resonance Raman analysis of trishomocubane and diamondoid dimers. J. Chem. Phys. 140, 034309-1–5, 2014
R. Meinke, R. Richter, A. Merli, A.A. Fokin, T.V. Koso, V.N. Rodionov, P.R. Schreiner, C. Thomsen, J. Maultzsch
(See online at https://doi.org/10.1063/1.4861758) - Electronic and vibrational properties of diamondoid oligomers. J. Phys. Chem., 2017
C. Tyborski, R. Gillen, A.A. Fokin, T.V. Koso, H. Hausmann, N.A. Fokina, V.N. Rodionov, P.R. Schreiner, C. Thomsen, J. Maultzsch
(See online at https://doi.org/10.1021/acs.jpcc.7b07666) - Transition metal complexes with cage-opened diamondoid tetracyclo[7.3.1.14,14.02,7]tetra-deca-6,11-diene. Functionalized Nanodiamonds, part 49. J. Coord. Chem. 68, 3295–3301, 2015
L. Valentin, A. Henss, B.A. Tkachenko, A.A. Fokin, P.R. Schreiner, S. Becker, C. Würtele, and S. Schindler
(See online at https://doi.org/10.1080/00958972.2015.1071802) - (1,3)Adamantano[2](2,7)pyrenophane, a Hydrocarbon with a Large Dipole Moment. Functionalized Nanodiamonds, part 55. Angew. Chem. Int. Ed. 55, 9277–9281, 2016
P. Kahl, J. P. Wagner, C. Balestrieri, J. Becker, H. Hausmann, G. J. Bodwell, and P.R. Schreiner
(See online at https://doi.org/10.1002/anie.201602201) - From isolated molecules to a van-der-Waals crystal: A theoretical and experimental analysis of a trishomocubane and a diamantane dimer in the gas and in the solid phase. Functionalized Nanodiamonds, part 59. J. Chem. Phys. 147, 044303, 2017
C. Tyborski, R. Meinke, R. Gillen, T. Zimmermann, A. Knecht, T. Rander, R. Richter, A. Merli, A.A. Fokin, T.V. Koso, V.N. Rodionov, P.R. Schreiner, T. Möller, C. Thomsen, and J. Maultzsch
(See online at https://doi.org/10.1063/1.4994898)
