Organic Semiconducting Materials from Sulfur-Hetero Benzo[k]fluoranthene Derivatives: Synthesis, Photophysical Properties, and Thin Film Transistor Fabrication

• Published in: Journal of organic chemistry Vol. 73; no. 14; pp. 5328 - 5339
• Main Authors: Yan, Qifan, Zhou, Yan, Ni, Ben-Bo, Ma, Yuguo, Wang, Jian, Pei, Jian, Cao, Yong
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 18.07.2008; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Condensed benzenic and aromatic compounds; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; AMBIPOLAR TRANSPORT; ROOM-TEMPERATURE; MOLECULAR-STRUCTURE; STAR-SHAPED OLIGOTHIOPHENES; CHARGE-TRANSPORT; HIGH-ELECTRON-MOBILITY; HIGH-PERFORMANCE SEMICONDUCTORS; DISCOTIC LIQUID-CRYSTALS; FIELD-EFFECT TRANSISTORS; THIOPHENE DERIVATIVES; Under vacuum; Configuration; Bromination; Iron III Chlorides; Organic sulfide; Thin film; Thiophene derivatives; Emission spectrometry; Optical properties; Dilute solution; Aromatic compound; Oxidation; Thermal annealing; Chemical synthesis; Semiconductor materials; Chloroform; Decarbonylation; Diels Alder addition; Air; X ray diffraction; Steady state; Chemical substitution; Chemical coupling; Suzuki coupling; Acetylene derivatives; Thermal properties; Field effect transistor; Absorption spectrometry; Sulfur heterocycle; Electrochemical properties; Cyclization; Morphology; Thin film transistor; Conjugated compound
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo800606b

A new family of air-stable sulfur-hetero oligoarenes based on the benzo[k]fluoranthene unit has been facilely developed as the active materials for thin film organic field-effect transistors. The Diels−Alder reaction between cyclopentadienone 1 and 2,2′-(ethyne-1,2-diyl)bisthiophene followed by decarbonylation afforded fluoranthene derivative 2. After bromination and subsequent substitution through Suzuki coupling reaction, the FeCl3-oxidative cyclization produced sulfur-hetero benzo[k]fluoranthene derivatives 8−12. In dilute chloroform solution, the absorption and emission behaviors of 2 and 4−7 showed characteristic features of the fluoranthene units, while their emission λmax red-shifted with an increase of the effective conjugation length. The steady state absorption and emission spectra of these newly synthesized compounds were thoroughly investigated and discussed. Thin film organic field-effect transistors (OFETs) using 8−11 as active materials were fabricated in a “top contact” configuration. Substituents at the skeleton play an important role in the film morphologies, which lead to different mobilities, while the charge mobilities of 8−11 from OFETs were improved after thermal annealing of the thin films. A carrier mobility as high as 0.083 cm2 V−1 s−1 and current on/off ratio of 106 were achieved through vacuum-deposited film followed by the thermal annealing process from 11.