Synergistic p-doping of polymer-wrapped small-diameter single-walled carbon nanotubes by tris(pentafluorophenyl)borane

Despite its comparatively low electron affinity, tris(pentafluorophenyl)borane (BCF) has been widely explored as an efficient molecular p-dopant for semiconducting polymers through the formation of Brønsted acidic complexes as well as its high affinity toward Lewis-basic nitrogen moieties. Many conj...

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Main Authors: Lindenthal, Sebastian (Author) , Rippel, Daniel (Author) , Kistner, Lucas (Author) , Hawkey, Angus (Author) , Zaumseil, Jana (Author)
Format: Article (Journal)
Language:English
Published: 20 March 2025
In: The journal of physical chemistry. C, Energy, materials, and catalysis
Year: 2025, Volume: 129, Issue: 11, Pages: 5520-5529
ISSN:1932-7455
DOI:10.1021/acs.jpcc.4c08584
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1021/acs.jpcc.4c08584
Verlag, kostenfrei, Volltext: https://pubs.acs.org/doi/10.1021/acs.jpcc.4c08584
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Author Notes:Sebastian Lindenthal, Daniel Rippel, Lucas Kistner, Angus Hawkey, and Jana Zaumseil

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520 |a Despite its comparatively low electron affinity, tris(pentafluorophenyl)borane (BCF) has been widely explored as an efficient molecular p-dopant for semiconducting polymers through the formation of Brønsted acidic complexes as well as its high affinity toward Lewis-basic nitrogen moieties. Many conjugated polymers that are used for selective wrapping and dispersion of semiconducting single-walled carbon nanotubes (SWCNTs) such as poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(6,6′-(2,2′-bipyridine))] (PFO-BPy) contain nitrogen moieties that should promote interaction with BCF. Here, we demonstrate that BCF indeed efficiently p-dopes even small-diameter (6,5) SWCNTs that are wrapped with large-bandgap PFO-BPy as corroborated by bleaching of the main absorption peaks and the appearance of red-shifted trion absorption and emission. In contrast, SWCNTs that are wrapped with poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO) without any Lewis-basic nitrogen moieties are only mildly doped. UV-Vis-NIR absorption, 19F NMR, and 11B NMR spectra confirm that BCF dopes the bipyridine-containing PFO-BPy but not PFO, thus leading to a proposed doping mechanism that relies on the unique interactions between BCF, the bipyridine moieties in PFO-BPy, and the nanotubes. Since BCF doping of PFO-BPy-wrapped (6,5) SWCNTs is more efficient than doping with F4TCNQ and more stable than doping with AuCl3, it provides a reliable alternative for spectroscopic studies of the interactions of charge carriers and excitons in SWCNTs. 
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