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- Title
Dithienyl Acenedithiophenediones as New π-Extended Quinoidal Cores: Synthesis and Properties.
- Authors
Kawabata, Kohsuke; Osaka, Itaru; Sawamoto, Masanori; Zafra, José L.; Mayorga Burrezo, Paula; Casado, Juan; Takimiya, Kazuo
- Abstract
We have synthesized two isomeric pairs of benzo- and naphthodithiophenediones with two flanking thiophenes and characterized them by single-crystal X-ray analysis, cyclic voltammetry, steady-state optical electronic absorption and emission spectroscopies, transient absorption spectroscopy, and vibrational spectroscopies with in situ spectroelectrochemistry techniques, and then compared them with the thieno[3,2- b]thiophene-2,5-dione counterpart that we previously reported. The results show that the central acenedithiophenedione cores have quinoidal conjugation with closed-shell character. The π-extension of the quinoidal core raises (lowers) the HOMO (LUMO) energy levels of the triads, resulting in the drastic reduction of their energy gaps from approximately 2.0 eV to 1.1 eV. Owing to the electron-withdrawing nature of the carbonyl terminal group at the quinoidal core, the triads have low-lying LUMO energy levels ranging from −3.9 eV to −4.3 eV, and can be regarded as strong electron-acceptor building units. Interestingly, the pairs of structural isomers have similar electronic structures in both the neutral and charged states despite the different shapes (linear and angular) and/or symmetry ( C2 h and C2 v) of the acenedithiophenedione cores.
- Subjects
SINGLE crystals; X-ray crystallography; CYCLIC voltammetry; ENERGY levels (Quantum mechanics); ELECTROPHILES
- Publication
Chemistry - A European Journal, 2017, Vol 23, Issue 19, p4579
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201605104