Short Excited-State Lifetimes Enable Photo-Oxidatively Stable Rubrene Derivatives

Abstract

A series of rubrene derivatives were synthesized and the influence of the side group in enhancing photooxidative stability was evaluated. Photo-oxidation half-lives were determined via UV−vis absorption spectroscopy, which revealed thiophene containing derivatives to be the most stable species. The electron affinity of the compounds did not correlate with stability as previously reported in literature. Our work shows that shorter excited-state lifetimes result in increased photo-oxidative stability in these rubrene derivatives. These results confirm that faster relaxation kinetics outcompete the formation of reactive oxygen species that ultimately degrade linear oligoacenes. This report highlights the importance of using molecular design to tune excited-state lifetimes in order to generate more stable oligoacenes.

Benzo- and Thieno-Annulated Tetracenes: A One-Pot Synthesis via Cross-Dehydrogenative Annulation

“…However, larger oligoacenes, such as tetracene and pentacene, suffer from significant practical drawbacks associated with, for example, a high susceptibility to engage in photochemical oxidation and dimerization reactions as well as limited solubility . For example, the representative tetracene derivative rubrene shows an exceptionally high charge-carrier mobility but simultaneously shows a high propensity to engage in rapid photooxidative degradation . Whereas a number of oligoacene derivatives have been intensively studied, the development of novel synthetic strategies for the versatile functionalization of acene derivatives and the improvement of their photooxidative stability remain of paramount importance for the continued progress of acene-based materials chemistry.…”

Significant energy gap modulation of sulfone-substituted benzosiloles: enhanced brightness and electron affinity for chemical vapor sensing, fingerprint detection and live-cell imaging

“…57 Compared with the reported rubrene and multi-acene derivatives, overall the benzosilole sulfone-based luminogens not only exhibit outstanding thermal stability but also possess photo- and photo-oxidization stability. 64,65…”

Research progress of rubrene as an excellent multifunctional organic semiconductor

“…This challenge has facilitated the development of rubrene derivatives / analogs, which was synthesized by introducing halogen or alkyl group into the side benzene ring or replacing the side benzene ring with other aromatic ring (thiophene, pyridine, etc.) [115][116][117][118]. For example, Li et al designed and synthesized a rubrene analogue 2,2′-(6,12-bis(perfluorophenyl)tetracene-5,11-diyl)dithiophene (SF 10 -RUB), exhibiting more inter-molecular interactions and lower HOMO energy levels compared with rubrene [118].…”