title: Multifunctional π-expanded macrocyclic oligothiophene 6-mers and related macrocyclic oligomers.
abstract: Multifunctional π-expanded macrocyclic oligothiophene 6-mer 1, as well as 9- (2) and 12-mers (3), was synthesized using a McMurry coupling reaction as the key step. The 6-mer 1 was converted to cyclo[6](2,5-thienylene-ethynylene) (4) by using a bromination-dehydrobromination procedure. From X-ray analysis, the crystal structures of nonplanar 1 and round-shaped 2 and 4 were elucidated. STM showed that 4 formed a self-assembled monolayer at the liquid/solid interface to produce a hexagonal porous network. Chemical oxidation of 1, 2, and 4 with 1 and 2 equiv of Fe(ClO4)3 produced 1(•+) and 1(2+), 2(•+) and 2(2+), and 4(•+) and 4(2+), respectively. Although oligothiophene radical cations containing β,β-disubstituted thiophenes usually do not form π-dimers, 4(•+) clearly formed a π-dimer owing to its planar, round shape. As for the dications of 1, 2, and 4, 1(2+), which has 34π-electrons, exhibited a large diatropic ring current effect, whereas 34π dication 4(2+) only showed a medium diatropic ring current effect. In contrast to 1(2+) and 4(2+), 52π dication 2(2+) had biradical cationic character instead of Hückel-type cyclic conjugation. Interestingly, 6-mer 1 showed polymorphism and unusual melting point behavior due to the number of stable conformations in the solid state. Single crystals of 1 melted at 176 °C, whereas an amorphous film of 1 crystallized in the temperature range of 80-83 °C to form a lamellarly stacked microcrystalline film, which melted at 139 °C. The polymorphism of 1 was applied to either fluorescence switching or switching of field effect transistor (FET) activity and electrical conductivity.
authors.affiliation: Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University , Hachioji, Tokyo 192-0397, Japan.
authors.forename: Masahiko
authors.initials: M
authors.lastname: Iyoda
authors.forename: Keita
authors.initials: K
authors.lastname: Tanaka
authors.forename: Hideyuki
authors.initials: H
authors.lastname: Shimizu
authors.forename: Masashi
authors.initials: M
authors.lastname: Hasegawa
authors.forename: Tohru
authors.initials: T
authors.lastname: Nishinaga
authors.forename: Tomohiko
authors.initials: T
authors.lastname: Nishiuchi
authors.forename: Yoshihito
authors.initials: Y
authors.lastname: Kunugi
authors.forename: Takayuki
authors.initials: T
authors.lastname: Ishida
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Otani
authors.forename: Hiroyasu
authors.initials: H
authors.lastname: Sato
authors.forename: Koji
authors.initials: K
authors.lastname: Inukai
authors.forename: Kazukuni
authors.initials: K
authors.lastname: Tahara
authors.forename: Yoshito
authors.initials: Y
authors.lastname: Tobe