title: Consecutive thiophene-annulation approach to π-extended thienoacene-based organic semiconductors with [1]benzothieno[3,2-b][1]benzothiophene (BTBT) substructure.
abstract: We describe a new synthetic route to the [1]benzothieno[3,2-b][1]benzothiophene (BTBT) substructure featuring two consecutive thiophene-annulation reactions from o-ethynyl-thioanisole substrates and arylsulfenyl chloride reagents that can be easily derived from arylthiols. The method is particularly suitable for the synthesis of unsymmetrical derivatives, e.g., [1]benzothieno[3,2-b]naphtho[2,3-b]thiophene, [1]benzothieno[3,2-b]anthra[2,3-b]thiophene, and naphtho[3,2-b]thieno[3,2-b]anthra[2,3-b]thiophene, a selenium-containing derivative, [1]benzothieno[3,2-b][1]benzoselenophene. It also allows us to access largely π-extended derivatives with two BTBT substructures, e.g., bis[1]benzothieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene and bis[1]benzothieno[2,3-d:2',3'-d']naphtho[2,3-b:6,7-b']dithiophene (BBTNDT). It should be emphasized that these new BTBT derivatives are otherwise difficult to be synthesized. In addition, since various substrates and reagents, o-ethynyl-thioanisoles and arylthiols, respectively, can be combined, the method can be regarded as a versatile tool for the development of thienoacene-based organic semiconductors in this class. Among the newly synthesized materials, highly π-extended BBTNDT afforded very high mobility (>5 cm(2) V(-1) s(-1)) in its vapor-deposited organic field-effect transistors (OFETs), which is among the highest for unsubstituted acene- or thienoacenes-based organic semiconductors. In fact, the structural analyses of BBTNDT both in the single crystal and thin-film state indicated that an interactive two-dimensional molecular array is realized in the solid state, which rationalize the higher carrier mobility in the BBTNDT-based OFETs.
authors.affiliation: Emergent Molecular Function Research Group, RIKEN Center for Emergent Matter Science (CEMS) , Wako, Saitama 351-0198, Japan.
authors.forename: Takamichi
authors.initials: T
authors.lastname: Mori
authors.forename: Takeshi
authors.initials: T
authors.lastname: Nishimura
authors.forename: Tatsuya
authors.initials: T
authors.lastname: Yamamoto
authors.forename: Iori
authors.initials: I
authors.lastname: Doi
authors.forename: Eigo
authors.initials: E
authors.lastname: Miyazaki
authors.forename: Itaru
authors.initials: I
authors.lastname: Osaka
authors.forename: Kazuo
authors.initials: K
authors.lastname: Takimiya