Theoretical and experimental studies on the effect of the 1,2-diketone group on geometry distortion for phenacene-type polycyclic aromatic compounds

Abstract This paper addresses the geometry distortion of orthoquinone-containing phenacene-type compounds by comparing the structures of phenanthrene-9,10-dione, chrysene-5,6-dione, and picene-13,14-dione. Interestingly, the calculated geometry of chrysene-5,6-dione under the isolated state was drastically different from the experimental one observed by single-crystal X-ray analysis. Theoretical calculations suggested that the molecular geometry of the o-quinone derivatives was sensitive not only to the sterically intramolecular proximity between the carbonyl oxygen and the hydrogen atoms of the benzene rings but also to intermolecular interactions. The twist distortion affects properties such as oscillator strength and 1-electron transitions, for low-lying excited states.