Electronic structure tuning of diamondoids through functionalization

We investigated the changes in electronic structures induced by chemical functionalization of the five smallest diamondoids using valence photoelectron spectroscopy. Through the variation of three parameters, namely functional group (thiol, hydroxy, and amino), host cluster size (adamantane, diamant...

Full description

Saved in:
Bibliographic Details
Published in:The Journal of chemical physics 2013-01, Vol.138 (2), p.024310-024310
Main Authors: Rander, Torbjörn, Staiger, Matthias, Richter, Robert, Zimmermann, Tobias, Landt, Lasse, Wolter, David, Dahl, Jeremy E, Carlson, Robert M K, Tkachenko, Boryslav A, Fokina, Natalie A, Schreiner, Peter R, Möller, Thomas, Bostedt, Christoph
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:We investigated the changes in electronic structures induced by chemical functionalization of the five smallest diamondoids using valence photoelectron spectroscopy. Through the variation of three parameters, namely functional group (thiol, hydroxy, and amino), host cluster size (adamantane, diamantane, triamantane, [121]tetramantane, and [1(2,3)4]pentamantane), and functionalization site (apical and medial) we are able to determine to what degree these affect the electronic structures of the overall systems. We show that unlike, for example, in the case of halobenzenes, the ionization potential does not show a linear dependence on the electronegativity of the functional group. Instead, a linear correlation exists between the HOMO-1 ionization potential and the functional group electronegativity. This is due to localization of the HOMO on the functional group and the HOMO-1 on the diamondoid cage. Density functional theory supports our interpretations.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4774268