Polycyclic Benzenoids: Why Kinked is More Stable than Straight

The enhanced stability of bent or kinked polycyclic benzenoids over linear ones is well established, phenanthrene and anthracene being archetypal representatives. The question why kinked is more stable than linear is, however, still a matter of discussion. Recently, it has been proposed that H-H bonding interactions between the two hydrogen atoms in the bay region of phenanthrene are responsible for the larger stability of this molecule as compared to anthracene. This conclusion conflicts with the vast body of evidence for nonbonded steric repulsion between these hydrogen atoms. In this work, we provide new, complementary evidence for the repulsive character of the H-H interactions in phenanthrene's bay region. We have traced the origin of phenanthrene's enhanced stability to the more efficient bonding in the π-electron system using, among others, a quantitative energy decomposition analysis of the bonding between the two constituting 2-methtriyl-phenyl fragments in both phenanthrene and anthracene (i.e., C14H10 = C6H4*-CH** + C6H4*-CH**). The scope of our study is extended to polycyclic benzenoids by analyzing also hexacene and various bent isomers of the latter. Our results once more falsify one of the core concepts of the theory of atoms-in-molecules (AIM), namely, that the presence of bond paths and the presence of bond critical points (they exist indeed between the two bay H atoms in phenanthrene) are sufficient indicators for a stabilizing interaction. Instead, our results confirm that these AIM parameters merely diagnose the proximity or contact between charge distributions, be this contact stabilizing or destabilizing.