Monoradicals and Diradicals of Dibenzofluoreno[3,2-b]fluorene Isomers: Mechanisms of Electronic Delocalization
| العنوان: | Monoradicals and Diradicals of Dibenzofluoreno[3,2-b]fluorene Isomers: Mechanisms of Electronic Delocalization |
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| المؤلفون: | Michael M. Haley, Carlos J. Gómez-García, Abel Cárdenas Valdivia, Ryohei Kishi, Hideki Hayashi, Yosuke Nakamura, Hidenori Miyauchi, Joshua E. Barker, Juan Casado, Shin-ichiro Kato, Samantha N. MacMillan, Masayoshi Nakano |
| المصدر: | Journal of the American Chemical Society. 142:20444-20455 |
| بيانات النشر: | American Chemical Society (ACS), 2020. |
| سنة النشر: | 2020 |
| مصطلحات موضوعية: | Anthracene, Diradical, General Chemistry, Fluorene, Carbocation, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Delocalized electron, Colloid and Surface Chemistry, chemistry, Computational chemistry, Structural isomer, Molecule, Carbanion |
| الوصف: | The preparation of a series of dibenzo- and tetrabenzo-fused fluoreno[3,2-b]fluorenes is disclosed, and the diradicaloid properties of these molecules are compared with those of a similar, previously reported series of anthracene-based diradicaloids. Insights on the diradical mode of delocalization tuning by constitutional isomerism of the external naphthalenes has been explored by means of the physical approach (dissection of the electronic properties in terms of electronic repulsion and transfer integral) of diradicals. This study has also been extended to the redox species of the two series of compounds and found that the radical cations have the same stabilization mode by delocalization that the neutral diradicals while the radical anions, contrarily, are stabilized by aromatization of the central core. The synthesis of the fluorenofluorene series and their characterization by electronic absorption and vibrational Raman spectroscopies, X-ray diffraction, SQUID measurements, electrochemistry, in situ UV-vis-NIR absorption spectroelectrochemistry, and theoretical calculations are presented. This work attempts to unify the properties of different series of diradicaloids in a common argument as well as the properties of the carbocations and carbanions derived from them. |
| تدمد: | 1520-5126 0002-7863 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_________::e587359751af38b3586b5b72b63032fa https://doi.org/10.1021/jacs.0c09588 |
| حقوق: | CLOSED |
| رقم الأكسشن: | edsair.doi...........e587359751af38b3586b5b72b63032fa |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 15205126 00027863 |
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