Forty years of Clar's aromatic pi-sextet rule

In 1972 Erich Clar formulated his aromatic pi-sextet rule that allows discussing qualitatively the aromatic character of benzenoid species. Now, 40 years later, Clar's aromatic pi-sextet rule is still a source of inspiration for many chemists. This simple rule has been validated both experimentally and theoretically. In this review, we select some particular examples to highlight the achievement of Clar's aromatic pi-sextet rule in many situations and we discuss two recent successful cases of its application.