Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes

Aya Yoshimura; Hitoshi Kimura; Kohei Kagawa; Mayuka Yoshioka; Toshiki Itou; Dhananjayan Vasu; Takashi Shirahata; Hideki Yorimitsu; Yohji Misaki

doi:10.3762/bjoc.16.86

Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes

Beilstein J Org Chem. 2020 May 12:16:974-981. doi: 10.3762/bjoc.16.86. eCollection 2020.

Authors

Aya Yoshimura^{1

2}, Hitoshi Kimura¹, Kohei Kagawa¹, Mayuka Yoshioka¹, Toshiki Itou¹, Dhananjayan Vasu³, Takashi Shirahata^{1

2}, Hideki Yorimitsu³, Yohji Misaki^{1

2}

Affiliations

¹ Department of Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan.
² Research Unit for Power Generation and Storage Materials, and Research Unit for Development of Organic Superconductors, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan.
³ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.

Abstract

Novel multistage redox tetrathiafulvalenes (TTFs) bearing 6-aryl-1,4-dithiafulvene moieties were synthesized by palladium-catalyzed direct C-H arylation. In the presence of a catalytic amount of Pd(OAc)₂, P(t-Bu₃)·HBF₄, and an excess of Cs₂CO₃, the C-H arylation of TTF with several aryl bromides bearing 1,3-dithiol-2-ylidenes took place efficiently to produce the corresponding π-conjugated molecules. We also succeeded in the estimation of the oxidation potentials and number of electrons involved in each oxidation step of the obtained compounds by digital simulations.

Keywords: cross-conjugated systems; digital simulation analysis; electrochemical properties; extended π-conjugation; tetrathiafulvalene.

Grants and funding

This work was partially supported by a Grant-in-Aid for Scientific Research (JP15H03798), from the Ministry of Education, Culture, Sports, Science and Technology (MEXT). This work was also supported by a Grant-in-Aid for Research Promotion, Ehime University, to The Research Unit for Development of Organic Superconductors and to The Research Unit for Power Generation and Storage Materials.