A Singular Molecule-to-Molecule Transformation on Video: The Bottom-Up Synthesis of Fullerene C60 from Truxene Derivative C60H30Click to copy article linkArticle link copied!
- Dominik Lungerich*Dominik Lungerich*Email: [email protected] (D.L.).Center for Nanomedicine (CNM), Institute for Basic Science (IBS), IBS Hall, 50 Yonsei-ro, Seodaemun-gu, Seoul, 03722, South KoreaGraduate Program of Nano Biomedical Engineering (NanoBME), Advanced Science Institute, Yonsei University, Seoul, 03722, South KoreaDepartment of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Dominik Lungerich
- Helen HoelzelHelen HoelzelDepartment of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanDepartment of Chemistry and Pharmacy, Organic Chemistry II, Friedrich-Alexander-University Erlangen-Nuernberg (FAU), Nikolaus-Fiebiger-Str. 10, 91058, Erlangen, GermanyMore by Helen Hoelzel
- Koji HaranoKoji HaranoDepartment of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Koji Harano
- Norbert JuxNorbert JuxDepartment of Chemistry and Pharmacy, Organic Chemistry II, Friedrich-Alexander-University Erlangen-Nuernberg (FAU), Nikolaus-Fiebiger-Str. 10, 91058, Erlangen, GermanyMore by Norbert Jux
- Konstantin Yu. AmsharovKonstantin Yu. AmsharovDepartment of Chemistry, Martin-Luther-University Halle-Wittenberg, Kurt-Mothes-Str. 2, 06120 Halle, GermanyMore by Konstantin Yu. Amsharov
- Eiichi Nakamura*Eiichi Nakamura*Email: [email protected] (E.N.).Department of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanMore by Eiichi Nakamura
Abstract
Singular reaction events of small molecules and their dynamics remain a hardly understood territory in chemical sciences since spectroscopy relies on ensemble-averaged data, and microscopic scanning probe techniques show snapshots of frozen scenes. Herein, we report on continuous high-resolution transmission electron microscopic video imaging of the electron-beam-induced bottom-up synthesis of fullerene C60 through cyclodehydrogenation of tailor-made truxene derivative 1 (C60H30), which was deposited on graphene as substrate. During the reaction, C60H30 transformed in a multistep process to fullerene C60. Hereby, the precursor, metastable intermediates, and the product were identified by correlations with electron dose-corrected molecular simulations and single-molecule statistical analysis, which were substantiated with extensive density functional theory calculations. Our observations revealed that the initial cyclodehydrogenation pathway leads to thermodynamically favored intermediates through seemingly classical organic reaction mechanisms. However, dynamic interactions of the intermediates with the substrate render graphene as a non-innocent participant in the dehydrogenation process, which leads to a deviation from the classical reaction pathway. Our precise visual comprehension of the dynamic transformation implies that the outcome of electron-beam-initiated reactions can be controlled with careful molecular precursor design, which is important for the development and design of materials by electron beam lithography.
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