Zethrenes, Extended p-Quinodimethanes, and Periacenes with a Singlet Biradical Ground State

Researchers have studied polycyclic aromatic hydrocarbons (PAHs) for more than 100 years, and most PAHs in the neutral state reported so far have a closed-shell electronic configuration in the ground state. However, recent studies have revealed that specific types of polycyclic hydrocarbons (PHs) could have a singlet biradical ground state and exhibit unique electronic, optical, and magnetic activities. With the appropriate stabilization, these new compounds could prove useful as molecular materials for organic electronics, nonlinear optics, organic spintronics, organic photovoltaics, and energy storage devices. However, before researchers can use these materials to design new devices, they need better methods to synthesize these molecules and a better understanding of the fundamental relationship between the structure and biradical character of these compounds and their physical properties. Their biradical character makes these compounds difficult to synthesize. These compounds are also challenging to physically characterize and require the use of various experimental techniques and theoretic methods to comprehensively describe their unique properties. In this Account, we will discuss the chemistry and physics of three types of PHs with a significant singlet biradical character, primarily developed in our group. These structures are zethrenes, Z-shaped quinoidal hydrocarbons; hydrocarbons that include a proaromatic extended p-quinodimethane unit; and periacenes, acenes fused in a peri-arrangement. We used a variety of synthetic methods to prepare these compounds and stabilized them using both thermodynamic and kinetic approaches. We probed their ground-state structures by electronic absorption, NMR, ESR, SQUID, Raman spectroscopy, and X-ray crystallography and also performed density functional theory calculations. We investigated the physical properties of these PHs using various experimental methods such as one-photon absorption, two-photon absorption, transient absorption spectroscopy, electrochemistry, and spectroelectrochemistry. These systematic studies revealed that aromaticity played a very important role in determining their singlet biradical character, which is critically related to both their physical properties and their chemical reactivity. In particular, we found that Clar's aromatic sextet rule, which is useful for the closed-shell PAHs, can also predict the relative biradical character of benzenoid PH-based singlet biradicaloids. Other factors, such as structural flexibility of the biradical and quinoid resonance forms and the participation of the substitution in the π-conjugation, also influence the biradical character. These molecular materials demonstrate a number of unique properties such as near-infrared absorption, redox amphotericity, large two-photon absorption cross section, short excited state lifetime, stimuli-responsive magnetic activity, and singlet fission, which suggests promise for future applications.