Enantiomeric Separation of Semiconducting Single-Walled Carbon Nanotubes by Acid Cleavable Chiral PolyfluoreneClick to copy article linkArticle link copied!
- Liang XuLiang XuInstitute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, GermanyMore by Liang Xu
- Michal Valášek*Michal Valášek*Email: [email protected]Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, GermanyMore by Michal Valášek
- Frank HennrichFrank HennrichInstitute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, GermanyInstitute of Quantum Materials and Technologies, Karlsruhe Institute of Technology, 76021 Karlsruhe, GermanyMore by Frank Hennrich
- Elaheh SedghamizElaheh SedghamizInstitute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, GermanyMore by Elaheh Sedghamiz
- Montserrat Penaloza-AmionMontserrat Penaloza-AmionInstitute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, GermanyMore by Montserrat Penaloza-Amion
- Daniel HäussingerDaniel HäussingerDepartment of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, SwitzerlandMore by Daniel Häussinger
- Wolfgang WenzelWolfgang WenzelInstitute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, GermanyMore by Wolfgang Wenzel
- Manfred M. Kappes*Manfred M. Kappes*Email: [email protected]Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, GermanyInstitute of Quantum Materials and Technologies, Karlsruhe Institute of Technology, 76021 Karlsruhe, GermanyInstitute of Physical Chemistry, Karlsruhe Institute of Technology, 76128 Karlsruhe, GermanyMore by Manfred M. Kappes
- Marcel Mayor*Marcel Mayor*Email: [email protected]Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, GermanyDepartment of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, SwitzerlandLehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou, Guangdong 510275, ChinaMore by Marcel Mayor
Abstract

Helical wrapping by conjugated polymer has been demonstrated as a powerful tool for the sorting of single-walled carbon nanotubes (SWCNTs) according to their electronic type, chiral index, and even handedness. However, a method of one-step extraction of left-handed (M) and right-handed (P) semiconducting SWCNTs (s-SWCNTs) with subsequent cleavage of the polymer has not yet been published. In this work, we designed and synthesized one pair of acid cleavable polyfluorenes with defined chirality for handedness separation of s-SWCNTs from as-produced nanotubes. Each monomer contains a chiral center on the fluorene backbone in the 9-position, and the amino and carbonyl groups in the 2- and 7-positions maintain the head-to-tail regioselective polymerization resulting in polyimines with strictly all-(R) or all-(S) configuration. The obtained chiral polymers exhibit a strong recognition ability toward left- or right-handed s-SWCNTs from commercially available CoMoCAT SWCNTs with a sorting process requiring only bath sonication and centrifugation. Interestingly, the remaining polymer on each single nanotube, which helps to prevent aggregation, does not interfere with the circular dichroism signals from the nanotube at all. Therefore, we observed all four interband transition peaks (E11, E22, E33, E44) in the circular dichroism (CD) spectra of the still wrapped optically enriched left-handed and right-handed (6,5) SWCNTs in toluene. Binding energies obtained from molecular dynamics simulations were consistent with our experimental results and showed a significant preference for one specific handedness from each chiral polymer. Moreover, the imine bonds along the polymer chains enable the release of the nanotubes upon acid treatment. After s-SWNT separation, the polymer can be decomposed into monomers and be cleanly removed under mild acidic conditions, yielding dispersant-free handedness sorted s-SWNTs. The monomers can be almost quantitatively recovered to resynthesize the chiral polymer. This approach enables high selective isolation of polymer-free s-SWNT enantiomers for their further applications in carbon nanotube (CNT) devices.
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