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Spectroscopy and Reactivity of Dialkoxy Acenes
Author(s) -
Brega Valentina,
Kanari Sare Nur,
Doherty Connor T.,
Che Dante,
Sharber Seth A.,
Thomas Samuel W.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901258
Subject(s) - acene , oxidizing agent , reactivity (psychology) , chemistry , photochemistry , density functional theory , singlet oxygen , alkoxy group , singlet state , alkylation , pentacene , spectroscopy , oxygen , computational chemistry , molecule , organic chemistry , alkyl , catalysis , excited state , medicine , alternative medicine , physics , thin film transistor , pathology , layer (electronics) , quantum mechanics , nuclear physics
Photochemical oxidation of acenes can benefit or impede their function, depending on the application. Although acenes with alkoxy substituents on reactive sites are important for applications as diverse as drug delivery and organic optoelectronics, the influence of chemical structure on their photochemical oxidation remains unknown. This paper therefore describes the synthesis, spectroscopic properties, and reactivity with singlet oxygen ( 1 O 2 ) of a series of dialkoxyacenes that vary in the number and types of fused rings in the (hetero)acene cores. Reductive alkylation of quinone precursors yielded target dialkoxyacenes with fused backbones ranging from benzodithiophene to tetracenothiophene. Trends of their experimental spectroscopic characteristics were consistent with time‐dependent density functional theory (TD‐DFT) calculations. NMR studies show that photochemically generated 1 O 2 oxidizes all but one of these acenes to the corresponding endoperoxides in organic solvent. The rates of these oxidations correlate with the number and types of fused arenes, with longer dialkoxyacenes generally oxidizing faster than shorter derivatives. Finally, irradiation of these acenes in acidic, oxidizing environments cleaves the ether bonds. This work impacts those working in organic optoelectronics, as well as those interested in harnessing photogenerated reactive oxygen species in functional materials.