Radical-enhanced intersystem crossing, spin dipolar interaction and electron exchange in perylenebisimide-TEMPO dyads
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Zhanjun Li
, Andrey A. Sukhanov
, Laura Bussotti
, Violeta K. Voronkova
, Mariangela Di Donato
und Yuki Kurashige
Abstract
4-Amino-2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical was linked to perylene-3,4:9,10-bis(dicarboximide) (PBI) at varying distances and orientations. PBI-TEMPO dyads with the radical linked at the bay-position show a charge transfer absorption band in the UV−vis absorption spectra. With increasing solvent polarity, a fluorescence quenching is observed for these dyads, whereas for a derivative with TEMPO attached at the imide-position, such polarity dependency for fluorescence spectra was not observed. Steady state and femtosecond/nanosecond time-resolved optical spectroscopy confirmed the occurrence of radical-enhanced intersystem crossing (REISC. kISC = (23 ps)−1 − (0.5 ns)−1). The lifetime of the 3*PBI state (τT = 1.0–7.6 μs) depends on the distance and orientations between TEMPO and PBI units. The results indicate that stronger electron spin–spin dipolar interaction (vdd) between the radical and the chromophore improve REISC efficiency. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy demonstrates different electron exchange interactions (JTR) in the dyads, varying from ferromagnetic interaction corresponding to strong exchange regime to weak antiferromagnetic exchange interaction with increasing the distance between PBI and TEMPO units. Transient-nutation experiments further clarify the TREPR signals. DFT calculations indicate that changes in the dyad structure alter the exchange coupling from ferromagnetic (JTR = 0.47 cm−1) to antiferromagnetic (JTR = −0.03 cm−1 and −0.01 cm−1).
Funding source: National Natural Science Foundation of China
Award Identifier / Grant number: 22473021 and U2001222
Funding source: Fundamental Research Funds for the Central Universities
Award Identifier / Grant number: DUT22LAB610
Funding source: National Key Research and Development Program of China
Award Identifier / Grant number: No. 2023YFE0197600
Funding source: Kazan Scientific Centre, Russian Academy of Sciences
Funding source: Research and Innovation Team Project of Dalian University of Technology
Award Identifier / Grant number: DUT2022TB10
Acknowledgments
J.Z. thanks the NSFC (22473021 and U2001222), the National Key Research and Development Program of China (the Ministry of Science and Technology, No. 2023YFE0197600), the Research and Innovation Team Project of Dalian University of Technology (DUT2022TB10), the Fundamental Research Funds for the Central Universities (DUT22LAB610) and the State Key Laboratory of Fine Chemicals for financial support. A.A.S. and V.K.V. acknowledge financial support from the government assignment for FRC Kazan Scientific Centre of RAS. M.D.D. thanks the European Union’s Horizon 2020 research and innovation program under grant agreement NO. 871124 Laser lab-Europe for the support.
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Research ethics: Not applicable.
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Informed consent: Not applicable.
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Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.
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Use of Large Language Models, AI and Machine Learning Tools: None declared.
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Conflict of interest: The authors state no conflict of interest.
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Research funding: J.Z. thanks the NSFC (22473021 and U2001222), the National Key Research and Development Program of China (the Ministry of Science and Technology, No. 2023YFE0197600), the Research and Innovation Team Project of Dalian University of Technology (DUT2022TB10), the Fundamental Research Funds for the Central Universities (DUT22LAB610) and the State Key Laboratory of Fine Chemicals for financial support. A.A.S. and V.K.V. acknowledge financial support from the government assignment for FRC Kazan Scientific Centre of RAS. M.D.D. thanks the European Union’s Horizon 2020 research and innovation program under grant agreement NO. 871124 Laser lab-Europe for the support.
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Data availability: The data that support the findings of this study are available in the Supporting Information of this article.
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