Synthesis, Stability, and Photochemistry of Pentacene, Hexacene, and Heptacene: A Matrix Isolation Study

Abstract

The photochemical bisdecarbonylation of bridged alpha-diketones (Strating-Zwanenburg reaction) to give the oligoacenes pentacene (2), hexacene (3), and heptacene (4) is investigated in solid inert gas matrices at cryogenic temperatures. The photodecomposition using visible light irradiation cleanly produces the corresponding oligoacene without formation of observable intermediates. This synthetic approach to the higher acenes allows a comprehensive comparative study of their electronic absorption and infrared spectral properties under identical conditions for the first time. In addition, the route makes it possible to investigate the thermal and photochemical stability of these higher acenes and addresses the problem of heptacene stability which dates back almost 70 years. This largest known member of the acene series is found to be unstable at room temperature. Furthermore, all oligoacenes 2-4 undergo a photoredox reaction upon 185 nm excitation, resulting in the concurrent formation of radical cations and anions in the noble gas matrix. These polaron states of the oligoacenes are stable under the conditions of their generation but collapse to the uncharged acenes upon visible light irradiation.