143034-07-5Relevant academic research and scientific papers
Spectroscopy and Reactivity of Dialkoxy Acenes
Brega, Valentina,Kanari, Sare Nur,Doherty, Connor T.,Che, Dante,Sharber, Seth A.,Thomas, Samuel W.
, p. 10400 - 10407 (2019/07/18)
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 (1O2) 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 1O2 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.
Novel ?-Extended Thiophene-Fused Electron Acceptors for Organic Metals
Cruz, Pilar de la,Martin, Nazario,Miguel, Fuencisla,Seoane, Carlos,Albert, Armando,et al.
, p. 6192 - 6198 (2007/10/02)
Novel ?-extended thiophene-fused TCNQ-type and DCNQI-type acceptors have been synthesized from the corresonding quinones by reaction with Lehnert's reagent and bis(trimetylsilyl)carbodiimide (BTC), respectively.Additionally, an example of the little-known hybrid TCNQ-DCNQI-type acceptor has also been obtained.The cyclic voltammetric data of the novel acceptors reveal two different behaviours for these molecules.The TCNQ-type derivatives exhibit a two-electron single-wave reduction to the dianion, as confirmed by controlled potential coulometry analysis.The DCNQI-type derivatives display two reduction waves to the corresponding radical anion and dianion.The same behaviour is shown by the hybrid TCNQ-DCNQI derivative.The acceptor ability is related to molecular planarity, and a comparative crystallographic study involving TCNQ-type and DCNQI-type derivatives (6a, 7a, and 8a) has been performed.
