373596-08-8Relevant articles and documents
Functionalized pentacene: Improved electronic properties from control of solid-state order [20]
Anthony,Brooks,Eaton,Parkin
, p. 9482 - 9483 (2001)
-
High ionization potential conjugated polymers
Kim, Youngmi,Whitten, James E.,Swager, Timothy M.
, p. 12122 - 12130 (2005)
We report the synthesis of a series of poly(p-phenylene ethynylene)s (PPEs) with high ionization potentials and associated high excited-state electron affinities. Their photophysical properties were investigated using steady-state and time-resolved fluorescence techniques. The ionization potentials of the polymer thin films were determined using ultraviolet photoelectron spectroscopy (UPS), and those with the highest ionization potentials displayed high sensitivity for the detection of electron-donating aromatic compounds. The effects of sterics, chemical structure, and electronic properties on the polymers' sensory responses were investigated by fluorescence quenching experiments in both solution and solid thin films. In addition, we report that in some cases the excited-state charge-transfer complexes (exciplexes) of the PPEs with analytes were observed. These latter effects provide promising opportunities for the formation of sensitive and selective chemical sensors.
Why triple bonds protect acenes from oxidation and decomposition
Fudickar, Werner,Linker, Torsten
supporting information, p. 15071 - 15082 (2012/11/06)
An experimental and computational study on the impact of functional groups on the oxidation stability of higher acenes is presented. We synthesized anthracenes, tetracenes, and pentacenes with various substituents at the periphery, identified their photooxygenation products, and measured the kinetics. Furthermore, the products obtained from thermolysis and the kinetics of the thermolysis are investigated. Density functional theory is applied in order to predict reaction energies, frontier molecular orbital interactions, and radical stabilization energies. The combined results allow us to describe the mechanisms of the oxidations and the subsequent thermolysis. We found that the alkynyl group not only enhances the oxidation stability of acenes but also protects the resulting endoperoxides from thermal decomposition. Additionally, such substituents increase the regioselectivity of the photooxygenation of tetracenes and pentacenes. For the first time, we oxidized alkynylpentacenes by using chemically generated singlet oxygen (1O2) without irradiation and identified a 6,13-endoperoxide as the sole regioisomer. The bimolecular rate constant of this oxidation amounts to only 1 × 10 5 s-1 M-1. This unexpectedly slow reaction is a result of a physical deactivation of 1O2. In contrast to unsubstituted or aryl-substituted acenes, photooxygenation of alkynyl-substituted acenes proceeds most likely by a concerted mechanism, while the thermolysis is well explained by the formation of radical intermediates. Our results should be important for the future design of oxidation stable acene-based semiconductors.
Unexpected formation of a cyclic vinylene sulfate in the synthesis of ethynyl-substituted acenes
Djukic, Brandon,Perepichka, Dmitrii F.
supporting information; experimental part, p. 6651 - 6653 (2012/07/27)
(E)-2-Styrylanthracene derivatives containing triisopropylsilylacetylene groups at the 9 and 10 positions were synthesized and characterized. The electronic properties have been studied by DFT calculations, spectroscopy and electrochemistry, revealing asymmetric resonance stabilization effects that result in the regioselective formation of an unusual cyclic vinylene sulfate.