Toward an Understanding of Diamond sp2-Defects with Unsaturated Diamondoid Oligomer Models

Tatyana S. Zhuk, Tetyana Koso, Alexander E. Pashenko, Ngo Trung Hok, Vladimir N. Rodionov, Michael Serafin, Peter R. Schreiner (Corresponding Author), Andrey A. Fokin (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

21 Citations (Scopus)


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.
Original languageEnglish
Pages (from-to)6577–6586
JournalJournal of the American Chemical Society
Issue number20
Publication statusPublished - May 2015
MoE publication typeA1 Journal article-refereed


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