Magnetic Bistability in an Organic Radical-Based Charge Transfer Cocrystal
We report herein an organic charge transfer cocrystal complex, consisting of a stable radical TPVr and an electron acceptor TCNQF 4 , as a rare sort of all-organic-based magnetic bistable materials with a thermally activated magnetic hysteresis loop over the temperature range from 170 to 260 K. Deta...
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| Published in: | Journal of the American Chemical Society Vol. 145; no. 44; pp. 24328 - 24337 |
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| Main Authors: | , , , , , , , , |
| Format: | Journal Article |
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American Chemical Society
08-11-2023
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| Abstract | We report herein an organic charge transfer cocrystal complex, consisting of a stable radical TPVr and an electron acceptor TCNQF 4 , as a rare sort of all-organic-based magnetic bistable materials with a thermally activated magnetic hysteresis loop over the temperature range from 170 to 260 K. Detailed X-ray crystallographic studies and theoretical calculations revealed that while a π-associated radical anion dimer was formed upon an integer charge transfer process from TPVr to the TCNQF 4 molecules within the cocrystal lattice, the resulting TCNQF 4 ·– π-dimers were found to exhibit varied intradimer π-stacking distances and singly occupied molecular orbital overlaps at different temperatures, thus yielding two different singlet states with distinct singlet–triplet gaps above and below the loop, which eventually contributed to the thermally excited molecular magnetic bistability. |
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| AbstractList | We report herein an organic charge transfer cocrystal complex, consisting of a stable radical TPVr and an electron acceptor TCNQF 4 , as a rare sort of all-organic-based magnetic bistable materials with a thermally activated magnetic hysteresis loop over the temperature range from 170 to 260 K. Detailed X-ray crystallographic studies and theoretical calculations revealed that while a π-associated radical anion dimer was formed upon an integer charge transfer process from TPVr to the TCNQF 4 molecules within the cocrystal lattice, the resulting TCNQF 4 ·– π-dimers were found to exhibit varied intradimer π-stacking distances and singly occupied molecular orbital overlaps at different temperatures, thus yielding two different singlet states with distinct singlet–triplet gaps above and below the loop, which eventually contributed to the thermally excited molecular magnetic bistability. We report herein an organic charge transfer cocrystal complex, consisting of a stable radical TPVr and an electron acceptor TCNQF4, as a rare sort of all-organic-based magnetic bistable materials with a thermally activated magnetic hysteresis loop over the temperature range from 170 to 260 K. Detailed X-ray crystallographic studies and theoretical calculations revealed that while a π-associated radical anion dimer was formed upon an integer charge transfer process from TPVr to the TCNQF4 molecules within the cocrystal lattice, the resulting TCNQF4·- π-dimers were found to exhibit varied intradimer π-stacking distances and singly occupied molecular orbital overlaps at different temperatures, thus yielding two different singlet states with distinct singlet-triplet gaps above and below the loop, which eventually contributed to the thermally excited molecular magnetic bistability. |
| Author | Xiao, Wang Zeng, Zebing Liu, Haohao Zhao, Longfeng Lai, Weiming Yang, Kun Xie, Sheng Bu, Yanru Guo, Jing |
| AuthorAffiliation | Shenzhen Research Institute of Hunan University State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering Hunan University School of Physics and Electronics |
| AuthorAffiliation_xml | – name: School of Physics and Electronics – name: Hunan University – name: Shenzhen Research Institute of Hunan University – name: State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering |
| Author_xml | – sequence: 1 givenname: Weiming surname: Lai fullname: Lai, Weiming organization: Shenzhen Research Institute of Hunan University – sequence: 2 givenname: Yanru surname: Bu fullname: Bu, Yanru organization: Shenzhen Research Institute of Hunan University – sequence: 3 givenname: Wang surname: Xiao fullname: Xiao, Wang organization: Shenzhen Research Institute of Hunan University – sequence: 4 givenname: Haohao surname: Liu fullname: Liu, Haohao organization: Shenzhen Research Institute of Hunan University – sequence: 5 givenname: Jing surname: Guo fullname: Guo, Jing organization: Shenzhen Research Institute of Hunan University – sequence: 6 givenname: Longfeng surname: Zhao fullname: Zhao, Longfeng organization: Hunan University – sequence: 7 givenname: Kun surname: Yang fullname: Yang, Kun organization: Shenzhen Research Institute of Hunan University – sequence: 8 givenname: Sheng orcidid: 0000-0003-1924-549X surname: Xie fullname: Xie, Sheng organization: Shenzhen Research Institute of Hunan University – sequence: 9 givenname: Zebing surname: Zeng fullname: Zeng, Zebing email: zbzeng@hnu.edu.cn organization: Shenzhen Research Institute of Hunan University |
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| CitedBy_id | crossref_primary_10_1002_adom_202400747 crossref_primary_10_1016_j_tet_2024_133929 |
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| Snippet | We report herein an organic charge transfer cocrystal complex, consisting of a stable radical TPVr and an electron acceptor TCNQF 4 , as a rare sort of... We report herein an organic charge transfer cocrystal complex, consisting of a stable radical TPVr and an electron acceptor TCNQF4, as a rare sort of... |
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| Title | Magnetic Bistability in an Organic Radical-Based Charge Transfer Cocrystal |
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