Toward an Understanding of Diamond sp(2)-Defects with Unsaturated Diamondoid Oligomer Models.

Nanometer-sized doubly bonded diamondoid dimers and trimers, which may be viewed as models of diamond with surface sp(2)-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.

Oxygen-doped nanodiamonds: synthesis and functionalizations.

Oxadiamondoids representing a new class of carbon nanoparticles were prepared from the respective diamondoid ketones via an effective two-step procedure involving addition of methyl magnesium iodide and oxidation with trifluoroperacetic acid in trifluoroacetic acid. The reactivities of the oxacages are determined by the position of the dopant and are in good agreement with computational predictions.