Journalartikel

Jahr der Veröffentlichung: 2015

Seiten: 6577-6586

Zeitschrift: Journal of the American Chemical Society

Bandnummer: 137

Heftnummer: 20

DOI Link: https://doi.org/10.1021/jacs.5b01555

Verlag: American Chemical Society

Abstract: 

Nanometer-sized doubly bonded diamondoid dimers and trimers, which may be viewed as models of diamond with surface sp²-defects,
were prepared from corresponding ketones via a McMurry coupling and
were characterized by spectroscopic and crystallographic methods. The
neutral hydrocarbons and their radical cations were studied utilizing
density functional theory (DFT) and ab initio (MP2) methods, which
reproduce the experimental geometries and ionization potentials well.
The van der Waals complexes of the oligomers with their radical cations
that are models for the self-assembly of diamondoids, form highly
delocalized and symmetric electron-deficient structures. This implies a
rather high degree of σ-delocalization within the hydrocarbons, not too
dissimilar to delocalized π-systems. As a consequence, sp²-defects
are thus also expected to be nonlocal, thereby leading to the observed
high surface charge mobilities of diamond-like materials. In order to be
able to use the diamondoid oligomers for subsequent surface attachment
and modification, their C—H-bond functionalizations were studied, and
these provided halogen and hydroxy derivatives with conservation of
unsaturation.

Harvard-Zitierstil: Zhuk, T., Koso, T., Pashenko, A., Hoc, N., Rodionov, V., Serafin, M., et al. (2015) Toward an Understanding of Diamond sp2-Defects with Unsaturated Diamondoid Oligomer Models, Journal of the American Chemical Society, 137(20), pp. 6577-6586. https://doi.org/10.1021/jacs.5b01555

APA-Zitierstil: Zhuk, T., Koso, T., Pashenko, A., Hoc, N., Rodionov, V., Serafin, M., Schreiner, P., & Fokin, A. (2015). Toward an Understanding of Diamond sp2-Defects with Unsaturated Diamondoid Oligomer Models. Journal of the American Chemical Society. 137(20), 6577-6586. https://doi.org/10.1021/jacs.5b01555