Ionic manipulation of charge-transfer and photodynamics of [60]fullerene confined in pyrrolo-tetrathiafulvalene cage

Steffen Bähring; Karina R. Larsen; Mustafa Supur; Kent A. Nielsen; Thomas Poulsen; Kei Ohkubo; Craig W. Marlatt; Eigo Miyazaki; Kazuo Takimiya; Amar H. Flood; Shunichi Fukuzumi; Jan O. Jeppesen

doi:10.1039/C7CC03775A

Ionic manipulation of charge-transfer and photodynamics of [60]fullerene confined in pyrrolo-tetrathiafulvalene cage†

Steffen Bähring,

‡^a Karina R. Larsen,‡^a Mustafa Supur,

§^b Kent A. Nielsen,^a Thomas Poulsen,^a Kei Ohkubo,

^c Craig W. Marlatt,^d Eigo Miyazaki,^e Kazuo Takimiya,

^f Amar H. Flood,

^d Shunichi Fukuzumi

*^gh and Jan O. Jeppesen

*^a

Author affiliations

* Corresponding authors

^a Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark
E-mail: joj@sdu.dk

^b Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

^c Institute for Advanced Co-Creation Studies, Open and Transdisciplinary Research Initiatives, Osaka University, Suita, Japan

^d Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA

^e Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan

^f Emergent Molecular Function Research Group, RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako, Saitama, Japan

^g Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea
E-mail: fukuzumi@chem.eng.osaka-u.ac.jp

^h Faculty of Science and Technology, Meijo University, SENTAN, JST, Nagoya, Aichi 468-8502, Japan

Abstract

A cage molecule incorporating three electron donating monopyrrolotetrathiafulvalene units was synthesised to host electron accepting [60]fullerenes. Formation of a strong 1 : 1 donor–acceptor (D–A) complex C₆₀⊂1 was confirmed by solid state X-ray analysis as well as ¹H NMR and absorption spectroscopic analyses of the arising charge-transfer (CT) band (λ = 735 nm, ε ≈ 840 M⁻¹ cm⁻¹). Inserting Li⁺ inside the [60]fullerene increased the binding 28-fold (K_a = 3.7 × 10⁶ M⁻¹) and a large bathochromic shift of the CT band to the near infrared (NIR) region (λ = 1104 nm, ε ≈ 4800 M⁻¹ cm⁻¹) was observed.

Chemical Communications

Ionic manipulation of charge-transfer and photodynamics of [60]fullerene confined in pyrrolo-tetrathiafulvalene cage†

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Ionic manipulation of charge-transfer and photodynamics of [60]fullerene confined in pyrrolo-tetrathiafulvalene cage

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