A Saturn-Like Complex Composed of Macrocyclic Oligothiophene and C60 Fullerene: Structure, Stability, and Photophysical Properties in Solution and the Solid State

Hideyuki Shimizu; Kyu Hyung Park; Hiroyuki Otani; Shinobu Aoyagi; Tohru Nishinaga; Yoshio Aso; Dongho Kim; Masahiko Iyoda

doi:10.1002/chem.201705565

A Saturn-Like Complex Composed of Macrocyclic Oligothiophene and C₆₀ Fullerene: Structure, Stability, and Photophysical Properties in Solution and the Solid State

Chemistry. 2018 Mar 12;24(15):3793-3801. doi: 10.1002/chem.201705565. Epub 2018 Feb 12.

Authors

Hideyuki Shimizu¹, Kyu Hyung Park², Hiroyuki Otani³, Shinobu Aoyagi⁴, Tohru Nishinaga¹, Yoshio Aso⁵, Dongho Kim², Masahiko Iyoda¹

Affiliations

¹ Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, Hachioji, Tokyo, 192-0397, Japan.
² Department of Chemistry and Spectroscopy Laboratory for, Functional π-Electronic Systems, Yonsei University, Seoul, 03722, Korea.
³ Graduate School of Environment and Information Sciences, Yokohama National University, Hodogaya-ku, Yokohama, Kanagawa, 240-8501, Japan.
⁴ Department of Information and Basic Science, Nagoya City University, Nagoya, 467-8501, Japan.
⁵ The Institute of Scientific and Industrial Research, Osaka University, Ibaraki, Osaka, 767-0047, Japan.

PMID: 29315942
DOI: 10.1002/chem.201705565

Abstract

A Saturn-like 1:1 complex composed of macrocyclic oligothiophene E-8T7A and C₆₀ fullerene (C₆₀ ) was synthesized to investigate the interaction between macrocyclic oligothiophenes and C₆₀ in solution and the solid state. Because the Saturn-like 1:1 complex E-8T7A⋅C₆₀ is mainly stabilized by van der Waals interactions between C₆₀ and the sulfur atoms of the E-8T7A macrocycle, C₆₀ is rather weakly incorporated inside the macro-ring in solution. However, in the solid state the Saturn-like 1:1 complex preferentially formed single crystals or nanostructured polymorphs. Interestingly, X-ray analysis and theoretical calculations exhibited hindered rotation of C₆₀ in the Saturn-like complex due to interactions between C₆₀ and the sulfur atoms. Furthermore, the photoinduced charge transfer (CT) interaction between E-8T7A and C₆₀ in solution was investigated by using femtosecond transient absorption (TA) spectroscopy. The ultrafast TA spectral changes in the photoinduced absorption bands were attributed to the CT process in the Saturn-like structure.

Keywords: inclusion compounds; macrocycles; structure elucidation; through-space interactions; time-resolved spectroscopy.