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https://doi.org/10.1039/c8sc01388h
Title: | Curved ?-conjugated corannulene dimer diradicaloids | Authors: | Wang, Q. Hu, P. Tanaka, T. Gopalakrishna, T.Y. Herng, T.S. Phan, H. Zeng, W. Ding, J. Osuka, A. Chi, C. Siegel, J. Wu, J. |
Issue Date: | 2018 | Publisher: | Royal Society of Chemistry | Citation: | Wang, Q., Hu, P., Tanaka, T., Gopalakrishna, T.Y., Herng, T.S., Phan, H., Zeng, W., Ding, J., Osuka, A., Chi, C., Siegel, J., Wu, J. (2018). Curved ?-conjugated corannulene dimer diradicaloids. Chemical Science 9 (22) : 5100-5105. ScholarBank@NUS Repository. https://doi.org/10.1039/c8sc01388h | Rights: | Attribution-NonCommercial 4.0 International | Abstract: | So far, most reported open-shell singlet diradicaloids are based on planar ?-conjugated molecules. Herein, we report the bridged corannulene dimer diradicaloids, Cor-D1 and Cor-D2, both showing a three-dimensional curved ?-conjugated structure. Cor-D1 has a small diradical character (y0 = 5.4%) and behaves more like a closed-shell quinoidal compound at room temperature, while Cor-D2 is a typical open-shell diradicaloid with a larger diradical character (y0 = 16.9%). Both compounds exhibited paramagnetic activity at elevated temperatures, with a singlet-triplet energy gap (?ES-T) of -8.4 and -3.0 kcal mol-1, respectively. X-ray crystallographic analysis revealed that both molecules have a dumbbell-shaped geometry, with the two terminal corannulene bowls bent to opposite directions. The spin is largely delocalized onto the two bowls in Cor-D2 and there are multiple [CH??] interactions between the neighboring bowls. Chemical oxidation/reduction to their respective dications/dianions results in global aromaticity with [4n + 2] ?-electrons delocalized through the periphery of the whole framework. © 2018 The Royal Society of Chemistry. | Source Title: | Chemical Science | URI: | https://scholarbank.nus.edu.sg/handle/10635/209679 | ISSN: | 2041-6520 | DOI: | 10.1039/c8sc01388h | Rights: | Attribution-NonCommercial 4.0 International |
Appears in Collections: | Elements Staff Publications |
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