title: Molecular Design and Syntheses of Tetracyano-5,10-porphyrinquinodimethane Showing Stabilized LUMO.
abstract: An isomer of tetracyanoporphyrinquinodimethane (TCPQ), 5,10-TCPQ, was designed, synthesized, and structurally characterized, and its basic properties were discussed with emphasis on comparison with those of reported 5,15-TCPQ. The title compound was synthesized by a convenient cascade reaction involving a catalyst-free aromatic nucleophilic substitution reaction and the Uno-Takahashi reaction. The obtained π-expanded redox molecule acted as a Wurster-type redox molecule that underwent not only reduction but also oxidation processes. Furthermore, its absorption spectrum showed a large bathochromic shift that extended to the near-IR region, approximately 1150 nm.
authors.affiliation: Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-Ohsawa, Hachi-Oji, Tokyo, 192-0397, Japan.
authors.forename: Ken-ichi
authors.initials: K
authors.lastname: Yamashita
authors.affiliation: Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-Ohsawa, Hachi-Oji, Tokyo, 192-0397, Japan.
authors.forename: Shino
authors.initials: S
authors.lastname: Sakamoto
authors.affiliation: Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-Ohsawa, Hachi-Oji, Tokyo, 192-0397, Japan.
authors.forename: Akihiro
authors.initials: A
authors.lastname: Suzuki
authors.affiliation: Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-Ohsawa, Hachi-Oji, Tokyo, 192-0397, Japan. sugiura@porphyrin.jp.
authors.forename: Ken-ichi
authors.initials: K
authors.lastname: Sugiura
keywords: absorption; density functional calculations; porphyrinoids; quinones; redox chemistry; reduction