Exploring the Threshold between Fullerenes and Nanotubes: Characterizing Isomerically Pure, Empty-Caged, and Tubular Fullerenes D 5 h -C 90 and D 5 d -C 100

• Published in: Journal of the American Chemical Society Vol. 144; no. 24; pp. 10825 - 10829
• Main Authors: Schüßlbauer, Christoph M., Krug, Marcel, Ullrich, Tobias, Franklin, Hannah M., Stevenson, Steven, Clark, Timothy, Guldi, Dirk M.
• Format: Journal Article
• Language: English
• Published: United States 22.06.2022
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.2c02442

We report the fully fledged photophysical characterization of isomerically pure, empty-caged, tubular fullerenes -C and -C and compare their key properties. In particular, the focus was on cage sizes between 60 and 150 carbon atoms with , , and symmetry. The optical band gap of -C is 1.65 eV, which is larger than 1.37 eV of -C . In stark contrast to the nonluminescent -C , -C luminesces at room temperature. Transient absorption spectroscopy shows that photoexcited -C is subject to a slow intersystem crossing that generates a triplet excited state. In contrast, a fast, nonradiative internal conversion governs the deactivation of -C : In this case, exploring the corresponding triplet excited state required triplet-triplet sensitization experiments with anthracene. Density functional theory calculations revealed the electronic structure of the fullertubes, and calculations are consistent with our experimental findings. The calculated band gap systematically decreases with the number of carbon atoms within the and series. In contrast, an oscillating behavior is noted within the series of fullertubes. Finally, photoexcited -C was found to undergo hole transfer with electron-donating triethylamines readily but not electron transfer with electron-accepting methyl viologens.