Ask Not How Many, But Where They Are: Substituents Control Energetic Ordering of Frontier Orbitals/Electronic Structures in Isomeric Methoxy-Substituted Dibenzochrysenes

Redox properties of polycyclic aromatic hydrocarbons (PAHs) can be modulated by substitution with electron-rich groups. Here we show, using the example of dibenzo­[g,p]­chrysene (DBC), that substitution position (i.e., meta vs para) alters the energetic ordering of frontier molecular orbitals (FMOs)...

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Bibliographic Details
Published in:Journal of physical chemistry. C 2018-02, Vol.122 (5), p.2539-2545
Main Authors: Ivanov, Maxim V., Talipov, Marat R., Navale, Tushar S., Rathore, Rajendra
Format: Article
Language:English
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Summary:Redox properties of polycyclic aromatic hydrocarbons (PAHs) can be modulated by substitution with electron-rich groups. Here we show, using the example of dibenzo­[g,p]­chrysene (DBC), that substitution position (i.e., meta vs para) alters the energetic ordering of frontier molecular orbitals (FMOs), leading to cation radicals with altered electronic structures and thereby redox/optical properties. In particular, incorporation of four methoxy groups in parent DBC at meta positions similarly impacts the energies of phenanthrene-like HOMO and biphenyl-like HOMO-1, while their incorporation at para position swaps energetic ordering of HOMO and HOMO-1. We demonstrate that a straightforward analysis of FMOs provides valuable insight toward the rational design of novel PAHs with tailored redox properties.
ISSN:1932-7447
1932-7455
DOI:10.1021/acs.jpcc.7b11232