Synthesis of Highly Distorted π-Extended [2.2]Metacyclophanes by Intermolecular Double Oxidative Coupling†
Yutaro Koyama
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)
Search for more papers by this authorCorresponding Author
Dr. Satoru Hiroto
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)Search for more papers by this authorCorresponding Author
Prof. Dr. Hiroshi Shinokubo
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)Search for more papers by this authorYutaro Koyama
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)
Search for more papers by this authorCorresponding Author
Dr. Satoru Hiroto
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)Search for more papers by this authorCorresponding Author
Prof. Dr. Hiroshi Shinokubo
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Aichi, 464-8603 (Japan)Search for more papers by this authorThis work was supported by Grants-in-Aid for Scientific Research (Nos. 22750036 and 24350023) from MEXT (Japan). H.S. also acknowledges the Toyoaki Scholarship Foundation for financial support.
Graphical Abstract
A strained relationship: Oxidation of dihydroxy-substituted acenes provides face-to-face [2.2]metacyclophane-like dimers (see scheme; O red, Si of iPr3Si groups blue). The products exhibited highly distorted structures caused by steric repulsion. UV/Vis and electrochemical analysis revealed that the HOMO–LUMO gap was decreased upon dimerization.
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