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Biradicaloid Behavior of a Twisted Double Bond

Cite this: J. Phys. Chem. Lett. 2021, 12, 19, 4729–4734
Publication Date (Web):May 13, 2021
https://doi.org/10.1021/acs.jpclett.1c00664
Copyright © 2021 American Chemical Society

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    Abstract

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    A compound with a highly twisted C═C bond in the intermediate bond dissociation region was isolated, and its biradicaloid nature was experimentally demonstrated. A bianthrone derivative substituted with long-chain alkoxy groups was synthesized, and its twisted conformer was assembled into crystals through hydrophobic intermolecular interactions of the introduced alkoxy chains. X-ray crystallography revealed that the C═C bond connecting the two anthrone rings has a long bond length (1.429 Å) and a large torsional angle (57.33°). In addition, ESR studies revealed that the twisted bianthrone has biradicaloid character with a small singlet–triplet energy gap of 23.8 kJ mol–1. The thermally excited triplet species were observed in the ESR spectrum as distinct fine structures along with a ΔMS = ±2 forbidden transition.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.1c00664.

    • Experimental procedures, synthesis, characterization, redox properties and CVs, computational details, structures and vibrational modes, NMR, UV–vis–NIR absorption, and ATR-FT-IR spectra, electronic transitions and oscillator strengths, ORTEP drawings, DSC, and geometries and energies (PDF)

    • Crystallographic data for 2 and 3 (CIF)

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    Cited By

    This article is cited by 11 publications.

    1. Yusuke Ishigaki, Takashi Harimoto, Takuya Shimajiri, Takanori Suzuki. Carbon-based Biradicals: Structural and Magnetic Switching. Chemical Reviews 2023, 123 (24) , 13952-13965. https://doi.org/10.1021/acs.chemrev.3c00376
    2. Tomohiko Nishiuchi, Seito Aibara, Hiroyasu Sato, Takashi Kubo. Synthesis of π-Extended Thiele’s and Chichibabin’s Hydrocarbons and Effect of the π-Congestion on Conformations and Electronic States. Journal of the American Chemical Society 2022, 144 (16) , 7479-7488. https://doi.org/10.1021/jacs.2c02318
    3. Marco B. S. Wonink, Brian P. Corbet, Artem A. Kulago, Gregory B. Boursalian, Bas de Bruin, Edwin Otten, Wesley R. Browne, Ben L. Feringa. Three-State Switching of an Anthracene Extended Bis-thiaxanthylidene with a Highly Stable Diradical State. Journal of the American Chemical Society 2021, 143 (43) , 18020-18028. https://doi.org/10.1021/jacs.1c05938
    4. Hao-Wen Kang, Yu-Chiao Liu, Wei-Kai Shao, Yu-Chen Wei, Chi-Tien Hsieh, Bo-Han Chen, Chih-Hsuan Lu, Shang-Da Yang, Mu-Jeng Cheng, Pi-Tai Chou, Ming-Hsi Chiang, Yao-Ting Wu. Synthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[a,i]fluorenylidene) and its derivatives. Nature Communications 2023, 14 (1) https://doi.org/10.1038/s41467-023-40990-8
    5. Tomohiko Nishiuchi, Kazuyuki Uchida, Takashi Kubo. Synthesis and structural evaluation of closed-shell folded and open-shell twisted hexabenzo[5.6.7]quinarene. Chemical Communications 2023, 59 (48) , 7379-7382. https://doi.org/10.1039/D3CC02157B
    6. Keisuke Ogumi, Kohki Nagata, Yuki Takimoto, Kentaro Mishiba, Yutaka Matsuo. Inkjet printing of mechanochromic fluorenylidene-acridane. Scientific Reports 2022, 12 (1) https://doi.org/10.1038/s41598-022-21600-x
    7. Keith Izod, Mo Liu, Peter Evans, Corinne Wills, Casey M. Dixon, Paul G. Waddell, Michael R. Probert. Spontaneous Decomposition of an Extraordinarily Twisted and Trans ‐Bent Fully‐Phosphanyl‐Substituted Digermene to an Unusual Ge I Cluster. Angewandte Chemie 2022, 134 (39) https://doi.org/10.1002/ange.202208851
    8. Keith Izod, Mo Liu, Peter Evans, Corinne Wills, Casey M. Dixon, Paul G. Waddell, Michael R. Probert. Spontaneous Decomposition of an Extraordinarily Twisted and Trans ‐Bent Fully‐Phosphanyl‐Substituted Digermene to an Unusual Ge I Cluster. Angewandte Chemie International Edition 2022, 61 (39) https://doi.org/10.1002/anie.202208851
    9. Yasukazu Hirao, Yosuke Hamamoto, Takashi Kubo. Tunable Solid‐State Thermochromism: Alkyl Chain Length‐Dependent Conformational Isomerization of Bianthrones. Chemistry – An Asian Journal 2022, 17 (11) https://doi.org/10.1002/asia.202200121
    10. Petri Murto, Hugo Bronstein. Electro-optical π-radicals: design advances, applications and future perspectives. Journal of Materials Chemistry C 2022, 10 (19) , 7368-7403. https://doi.org/10.1039/D1TC05268C
    11. Tomohiko Nishiuchi, Seito Aibara, Takuya Yamakado, Ryo Kimura, Shohei Saito, Hiroyasu Sato, Takashi Kubo. Sterically Frustrated Aromatic Enes with Various Colors Originating from Multiple Folded and Twisted Conformations in Crystal Polymorphs**. Chemistry – A European Journal 2022, 28 (28) https://doi.org/10.1002/chem.202200286

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