Synthesis and Strong π-π Interaction of Hexaazatriphenylene Derivatives with Alternating Electron-Withdrawing and -Donating Groups

Akira Hinokimoto; Toshinori Ono; Makoto Fujiwara; Hiroki Mori; Ryohei Akiyoshi; Shinya Nakamura; Osamu Tsutsumi; Akinori Saeki; Yasutaka Kitagawa; Satoshi Horike; Daisuke Tanaka

doi:10.1002/asia.202200225

Synthesis and Strong π-π Interaction of Hexaazatriphenylene Derivatives with Alternating Electron-Withdrawing and -Donating Groups

Chem Asian J. 2022 Jun 1;17(11):e202200225. doi: 10.1002/asia.202200225. Epub 2022 Apr 27.

Authors

Akira Hinokimoto^{1

2}, Toshinori Ono¹, Makoto Fujiwara¹, Hiroki Mori¹, Ryohei Akiyoshi¹, Shinya Nakamura³, Osamu Tsutsumi³, Akinori Saeki⁴, Yasutaka Kitagawa⁵, Satoshi Horike^{2

6

7}, Daisuke Tanaka¹

Affiliations

¹ Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan.
² Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto, 615-8510, Japan.
³ Department of Applied Chemistry, Ritsumeikan University, Kusatsu, 525-8577, Japan.
⁴ Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
⁵ Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama-cho, Toyonaka, Osaka 560-8531, Japan.
⁶ Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University, Kyoto, 606-8501, Japan.
⁷ Department of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, 21210, Thailand.

PMID: 35434893
DOI: 10.1002/asia.202200225

Abstract

Hexaazatriphenylene (HAT) derivatives have attracted wide attention because of their electron-deficient nature and unique self-assembly properties. In this work, a facile synthesis method for obtaining HAT derivatives with alternating electron-withdrawing nitrile and electron-donating alkoxy groups (HATCNOCn) is proposed. Crystal structure analysis indicated that HATCNOCn forms a one-dimensional columnar structure via strong π-π interactions. Density functional theory calculations revealed that the edge of HATCNOCn is divided into positively and negatively charged sites owing to the presence of alternating nitrile and alkoxy groups, which would induce strong π-π interactions. Thermal analysis and polarizing optical microscopy revealed that HATCNOCn exhibits columnar liquid-crystal phases. Time-resolved microwave conductivity measurements further demonstrated the photoconductive nature of HATCNOCn. The proposed strategy could provide a new strategy for the design of novel organic semiconductive materials.

Keywords: aromatic interaction; columnar structure; coordination polymers; hexaazatriphenylene; photoconductivity.

Abstract

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