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Exploring the Threshold between Fullerenes and Nanotubes: Characterizing Isomerically Pure, Empty-Caged, and Tubular
Christoph M Schüßlbauer1, Marcel Krug1, Tobias Ullrich1
1Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, Erlangen 91058, Germany.
Journal of the American Chemical Society
|June 8, 2022
Summary
We characterized tubular fullerenes D5-C90 and D5-C100, finding D5-C100 luminesces and exhibits hole transfer, unlike nonluminescent D5-C90. Density functional theory calculations supported these photophysical property differences.
Area of Science:
- Materials Science
- Physical Chemistry
- Nanotechnology
Background:
- Fullerenes are allotropes of carbon with unique electronic and optical properties.
- Tubular fullerenes, or fullertubes, offer tunable properties based on size and symmetry.
- Understanding the photophysics of specific fullerene structures is crucial for their application.
Purpose of the Study:
- To conduct a comprehensive photophysical characterization of isomerically pure, empty-caged, tubular fullerenes D5-C90 and D5-C100.
- To compare the optical and excited-state properties of these fullertubes.
- To elucidate the electronic structure and deactivation pathways of photoexcited fullertubes using experimental and computational methods.
Main Methods:
- Synthesis and isolation of isomerically pure D5-C90 and D5-C100 fullertubes.
- Steady-state and time-resolved spectroscopy (UV-Vis absorption, photoluminescence, transient absorption).
- Density Functional Theory (DFT) calculations for electronic structure and band gap determination.
- Triplet-triplet sensitization experiments.
- Photoinduced electron and hole transfer studies.
Main Results:
- D5-C100 exhibits a larger optical band gap (1.65 eV) than D5-C90 (1.37 eV).
- D5-C100 is luminescent at room temperature, while D5-C90 is not.
- Photoexcited D5-C100 undergoes slow intersystem crossing to a triplet state, whereas D5-C90 deactivates via fast, non-radiative internal conversion.
- DFT calculations confirmed experimental findings, showing a systematic decrease in band gap with size for D3/D3' series and oscillating behavior for D5 series.
- D5-C100 readily undergoes hole transfer with triethylamines but not electron transfer with methyl viologens.
Conclusions:
- The photophysical properties of tubular fullerenes are highly dependent on cage size and symmetry.
- D5-C100 possesses distinct excited-state dynamics and luminescence compared to D5-C90.
- The electronic structure calculations align with experimental observations, providing insights into structure-property relationships.
- Tubular fullerenes like D5-C100 show potential for applications involving charge transfer processes.
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