Nanohoops Favour Light-Induced Energy Transfer over Charge Separation in Porphyrin/[10]CPP/Fullerene Rotaxanes.

Autor: Schwer F; Institute of Organic Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany., Zank S; Department of Chemistry and Pharmacy, FAU Profile Center Solar, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany., Freiberger M; Department of Chemistry and Pharmacy, FAU Profile Center Solar, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany., Steudel FM; Institute of Organic Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany., Geue N; Michael Barber Centre for Collaborative Mass Spectrometry, Manchester Institute of Biotechnology, Department of Chemistry, The University of Manchester, 131 Princess Street, Manchester, M1 7DN, UK., Ye L; Department of Chemistry and Pharmacy, FAU Profile Center Solar, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany., Barran PE; Michael Barber Centre for Collaborative Mass Spectrometry, Manchester Institute of Biotechnology, Department of Chemistry, The University of Manchester, 131 Princess Street, Manchester, M1 7DN, UK., Drewello T; Department of Chemistry and Pharmacy, FAU Profile Center Solar, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany., Guldi DM; Department of Chemistry and Pharmacy, FAU Profile Center Solar, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany., von Delius M; Institute of Organic Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2025 Jan 02; Vol. 64 (1), pp. e202413404. Date of Electronic Publication: 2024 Nov 11.
DOI: 10.1002/anie.202413404
Abstrakt: [2]Rotaxanes offer unique opportunities for studying and modulating charge separation and energy transfer, because the mechanical bond allows the robust, yet spatially dynamic tethering of photoactive groups. In this work, we synthesized [2]rotaxane triads comprising a central (aza)[10]CPP⊃C 60 bis-adduct complex and two zinc porphyrin stoppers to address how the movable nanohoop affects light-induced charge separation and energy transfer between the rotaxane subcomponents. We found that neither the parent nanohoop [10]CPP nor its electron-deficient analogue aza[10]CPP actively participate in charge separation. In contrast, the nanohoops completely prevented through-space charge separation. This result is likely due to supramolecular "shielding", because charge separation was observed in the thread that acted as reference dyad. On the other hand, the suppression of electron transfer allowed the observation of energy transfer from the porphyrin triplet to the fullerene triplet state with a lifetime of ca. 25 μs. The presence of the interlocked nanohoops therefore leads to a dramatic switch between charge separation and energy transfer. We suggest that our results explain observations made by others in photovoltaic devices comprising nanohoops and may pave the way toward strategic uses of mechanically interlocked architectures in devices that feature (triplet) energy transfer.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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