Generalized kekulenes and clarenes as novel families of cycloarenes: structures, stability, and spectroscopic properties.

ABSTRACT

Cycloarenes constitute a captivating class of polycyclic aromatic hydrocarbons with unique structures and properties, but their synthesis represents a challenging task in organic chemistry. Kekulenes and edge-extended kekulenes as classic types of cycloarenes play an important role in the comprehension of π electron distribution, but their sparse molecular diversity considerably limits their further development and application. In this work, we propose two novel classes of cycloarenes, the generalized kekulenes and the clarenes. Using density functional theory, we carry out a comprehensive study of all possible isomers of the generalized kekulenes and clarenes with different sizes. By applying a simple Hückel model, we show that π delocalization plays a crucial role in determining the relative stability of isomers. We also discover that π-π stacking is commonly present in certain larger clarenes and provides a considerable additional stabilization effect, making the corresponding isomers the lowest-energy ones. Among all considered typical looped polyarenes, generalized kekulenes and/or clarenes are revealed to be the energetically most stable forms, suggesting that these novel cycloarenes proposed here would be viable targets for future synthetic work. The simulated 1H NMR spectra and UV-vis absorption spectra provide valuable information about the electronic and optoelectronic properties for the most stable generalized kekulene and clarene species and may support their identification in future synthesis and experimental characterization.