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Stepwise reduction of an asymmetric π-expanded pyracylene towards the crystalline radical trianion

The chemical reduction of a pyracylene-hexa-peri-hexabenzocoronene-(HBC)-fused nanographene TPP was investigated with K and Rb metals to reveal its multi-electron acceptor abilities. The in situ reaction of TPP with the above alkali metals, monitored by UV-vis-NIR and 1H NMR spectroscopy, evidenced...

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Bibliographic Details
Main Authors: Zhu, Yikun (Author) , Borstelmann, Jan (Author) , Neiss, Christian (Author) , Wei, Zheng (Author) , Görling, Andreas (Author) , Kivala, Milan (Author) , Petrukhina, Marina A. (Author)
Format: Article (Journal)
Language:English
Published: 13 January 2025
In: Chemical science
Year: 2025, Volume: 16, Issue: 7, Pages: 3211-3217
ISSN:2041-6539
DOI:10.1039/D4SC08255A
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1039/D4SC08255A
Verlag, kostenfrei, Volltext: https://pubs.rsc.org/en/content/articlelanding/2025/sc/d4sc08255a
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Author Notes:Yikun Zhu, Jan Borstelmann, Christian Neiss, Zheng Wei, Andreas Görling, Milan Kivala, and Marina A. Petrukhina
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Summary:The chemical reduction of a pyracylene-hexa-peri-hexabenzocoronene-(HBC)-fused nanographene TPP was investigated with K and Rb metals to reveal its multi-electron acceptor abilities. The in situ reaction of TPP with the above alkali metals, monitored by UV-vis-NIR and 1H NMR spectroscopy, evidenced the stepwise reduction process. The use of different solvents and secondary ligands enabled isolation of single crystals of three different reduced states of TPP with 1, 2, and 3 electrons added to its π-system. This provided a unique set of carbanions with gradually increasing negative charge for in-depth structural analysis of the outcomes of controlled electron addition to a non-planar and asymmetric nanographene, using X-ray crystallographic, spectroscopic, and theoretical tools. EPR spectroscopy measurements of the mono- and triply-reduced TPP products revealed distinct EPR splitting patterns. DFT calculations demonstrated a notable difference in the spin density distribution of these two open-shell products and provided insights into experimental EPR data. Moreover, the influence of the counterions on the “naked” TPP anions was illustrated computationally.
Item Description:Gesehen am 21.08.2025
Physical Description:Online Resource
ISSN:2041-6539
DOI:10.1039/D4SC08255A

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