Evolution of excess electron binding motifs under both internal‐push (from exo C–F bonds) and external‐push (from endo C–F bonds) electron effects in endohedral metallofullerenes with endo C–F bonds |
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| Authors: | Yin‐Feng Wang Qing Wang Zhuo Li Zhi‐Ru Li Jiangen Huang Jiuhui Liu Guangpei Zhou |
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| Institution: | 1. Jiangxi Province Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Jinggangshan University, , Ji'an, Jiangxi, 343009 China;2. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry Jilin University, , Changchun, 130023 China |
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| Abstract: | How does the endo C–F bond influence the excess electron binding motif? For lithium‐doped endohedral perfluorofullerenes with endo C–F bonds, under both internal‐push (from exo C–F bonds) and external‐push (from endo C–F bonds) electron effects, the singly occupied molecular orbital electron cloud of the sphere‐like Li···F8@C60F52 (D2) is partially dispersed within the σp–s antibonding orbital of endo C–F bonds and the space between Cδ+–Fendoδ– double electric layers, which makes Li···F8@C60F52 have partial excess electron (electride characteristics) and partial lithium salt characteristics, while in the tube‐like Li···F2@C60F58 (Cs), as the Li is changing from approaching F to keeping away from F and to approaching another one, the singly occupied molecular orbital electron cloud is mainly dispersed from within the p orbital of the short endo C–F bond to within the middle of the two F atoms and again to within the p orbital of the short endo C–F bond, which indicates an evolution from lithium salt characteristic to excess electron characteristic, and again to lithium salt characteristic. Copyright © 2012 John Wiley & Sons, Ltd. |
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| Keywords: | binding motif endohedral perfluorofullerene excess electron external‐push electron effect internal‐push electron effect |
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