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See Supporting Information
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Local strain as measured by the pyramidalization angle (PA) is also an important factor determining the reactivity of fullerenes. The PA for carbons within the four-membered ring of 2 is 17.9°, much larger than for fullerenes and organic molecules that can be isolated in the condensed phase (PA ≤ 13°, the PA for a tetrahedral carbon is 19.5°!), see: Haddon, R. C.; Scuseria, G. E.; Smalley, R. E. Chem. Phys. Lett. 1997, 272, 38-42.
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0342569986
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note
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RHF/6-31G* single-point energies also yield a significant decrease (1.3 eV) in HOMO-LUMO gap of 2 relative to 1. Also, RHF/6-31G* single-point calculations yield very similar FMO distributions in 1 and 2, compared to the B3LYP/6-31G* results.
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0343004356
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unpublished
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2 (Py = 2-pyridyl) in solution using a very similar mechanism and shown by X-ray crystallography that it has a cyclobutene ring. Qian, W.; Amador, R.; Comito, A.; Jarrosson, T.; Sander, M.; Verheul, S.; Khan, S. I.; Rubin, Y., unpublished.
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Rubin, Y.8
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