| Autor: |
Teunissen JL; Research Group of General Chemistry, Vrije Universiteit Brussel (VUB) , Pleinlaan 2, 1050 Brussels, Belgium., De Proft F; Research Group of General Chemistry, Vrije Universiteit Brussel (VUB) , Pleinlaan 2, 1050 Brussels, Belgium., De Vleeschouwer F; Research Group of General Chemistry, Vrije Universiteit Brussel (VUB) , Pleinlaan 2, 1050 Brussels, Belgium. |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of chemical theory and computation [J Chem Theory Comput] 2017 Mar 14; Vol. 13 (3), pp. 1351-1365. Date of Electronic Publication: 2017 Feb 28. |
| DOI: |
10.1021/acs.jctc.6b01074 |
| Abstrakt: |
Functionalized diamondoids show great potential as building blocks for various new optoelectronic applications. However, until now, only simple mono and double substitutions were investigated. In this work, we considered up to 10 and 6 sites for functionalization of the two smallest diamondoids, adamantane and diamantane, respectively, in search for diamondoid derivatives with a minimal and maximal HOMO-LUMO energy gap. To this end, the energy gap was optimized systematically using an inverse molecular design methodology based on the best-first search algorithm combined with a Monte Carlo component to escape local optima. Adamantane derivatives were found with HOMO-LUMO gaps ranging from 2.42 to 10.63 eV, with 9.45 eV being the energy gap of pure adamantane. For diamantane, similar values were obtained. The structures with the lowest HOMO-LUMO gaps showed apparent push-pull character. The push character is mainly formed by sulfur or nitrogen dopants and thiol groups, whereas the pull character is predominantly determined by the presence of electron-withdrawing nitro or carbonyl groups assisted by amino and hydroxyl groups via the formation of intramolecular hydrogen bonds. In contrast, maximal HOMO-LUMO gaps were obtained by introducing numerous electronegative groups. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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