Interfullerene Electronic Interactions and Excited-State Dynamics in Fullerene Dumbbell Conjugates

Yongqiang Chai; Liping Liu; Yanjun Xu; Xiaolong Liu; Chong Wang; Yifan Bo; Yuhe Zhang; Zhuan Wang; Yuxiang Weng; Dirk M Guldi; Bo Wu; Chunru Wang

doi:10.1021/jacs.3c03486

Interfullerene Electronic Interactions and Excited-State Dynamics in Fullerene Dumbbell Conjugates

J Am Chem Soc. 2023 Jul 5;145(26):14190-14195. doi: 10.1021/jacs.3c03486. Epub 2023 Jun 13.

Authors

Yongqiang Chai^{1

2}, Liping Liu^{1

3}, Yanjun Xu^{4

5}, Xiaolong Liu¹, Chong Wang^{1

5}, Yifan Bo², Yuhe Zhang^{1

5}, Zhuan Wang^{4

5}, Yuxiang Weng^{4

5}, Dirk M Guldi², Bo Wu^{1

5}, Chunru Wang^{1

5}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
² Department of Chemistry and Pharmacy and Interdisciplinary Center of Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany.
³ Department of Chemistry, Tsinghua University, Beijing 100084, China.
⁴ Beijing National Laboratory for Condensed Matter Physics, CAS Key Laboratory of Soft Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
⁵ University of Chinese Academy of Sciences, Beijing 100049, China.

PMID: 37310385
DOI: 10.1021/jacs.3c03486

Abstract

Several dumbbell conjugates featuring M₃N@I_h-C₈₀ (M = Sc, Y) and C₆₀ were prepared to systematically investigate interfullerene electronic interactions and excited state dynamics. From electrochemical investigations, we concluded that the redox potentials of our M₃N@I_h-C₈₀ (M = Sc, Y) dumbbells depend largely on the interfullerene electronic interactions. Assisted by DFT calculation, the unique role of metal atoms was highlighted. Most importantly, ultrafast spectroscopy experiments revealed symmetry-breaking charge separation in Sc₃N@C₈₀-dumbbell to yield an unprecedented (Sc₃N@C₈₀)^•+-(Sc₃N@C₈₀)^•- charge separated state. This is, to the best of our knowledge, the first time that symmetry-breaking charge separation following photoexcitation is corroborated in a fullerene system. As such, our work shed light on the significance of interfullerene electronic interactions and their uniqueness for modulating excited state properties.