Biased Bowl-Direction of Monofluorosumanene in the Solid State

Yumi Yakiyama; Minghong Li; Dongyi Zhou; Tsuyoshi Abe; Chisato Sato; Kohei Sambe; Tomoyuki Akutagawa; Teppei Matsumura; Nobuyuki Matubayasi; Hidehiro Sakurai

doi:10.1021/jacs.3c11311

Biased Bowl-Direction of Monofluorosumanene in the Solid State

J Am Chem Soc. 2024 Feb 28;146(8):5224-5231. doi: 10.1021/jacs.3c11311. Epub 2024 Feb 19.

Authors

Yumi Yakiyama^{1

2}, Minghong Li¹, Dongyi Zhou¹, Tsuyoshi Abe¹, Chisato Sato³, Kohei Sambe³, Tomoyuki Akutagawa^{3

4}, Teppei Matsumura⁵, Nobuyuki Matubayasi⁵, Hidehiro Sakurai^{1

2}

Affiliations

¹ Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
² Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
³ Graduate School of Engineering, Tohoku University, 6-6 Aramakiazaaoba, Aoba-ku, Sendai 980-8579, Japan.
⁴ Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan.
⁵ Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan.

Abstract

A new curved π-conjugated molecule 1-fluorosumanene (1) was designed and synthesized that possesses one fluorine atom on the benzylic carbon of sumanene. This compound can exhibit bowl inversion in solution, leading to the formation of two diastereomers, 1_endo and 1_exo, with different dipole moments. Experimental and theoretical investigation revealed an energetical relationship among 1_exo, 1_endo, and solvent to realize the various endo:exo ratios in the single crystals of 1 depending on the crystallization solvent. Significantly, the molecular dynamics (MD) simulations revealed that 1_exo positively worked for the elongation of the stacking structure and the final endo:exo ratio was affected by the relative stability difference between 1_endo and 1_exo derived by solvation. Such an arrangeable endo:exo ratio of 1 realized the preparation of unique materials showing a different dielectric response from the same molecule 1 just by changing the crystallization solvent.