We report the F2 @C60 system as the first example of an endohedral fullerene in which C60 acts as a cation C60 + interacting with endohedral anion, F2 - . Our state-of-the-art computations reveal that in F2 @C60 , despite of the known high electron affinity of C60 , an electron is transferred from C60 to F2 resulting in the F2 - @C60 + system. The F-F bond length in F2 @C60 is substantially longer than in free F2 , which is the result of electron-transfer to the antibonding σu molecular orbital of F2 . Interestingly, although there is a full charge-transfer of one electron between C60 and F2 , only negligible delocalized covalent interactions are found between F2 - and C60 + which is a reminiscent of ionic crystals. Therefore, F2 - @C60 + can be considered as a single-molecule crystal. The other encapsulated halogens in C60 do not show such behavior.

Departamento de Química Orgánica 1 and Centro de Innovación en Química Avanzada Facultad de Ciencias Químicas Universidad Complutense de Madrid 28040 Madrid Spain

Department of Chemistry Faculty of Science Masaryk University Kamenice 5 62500 Brno Czech Republic

Donostia International Physics Center P K 1072 20080 Donostia Euskadi Spain

Fachbereich Chemie Philipps Universität Marburg Hans Meerwein Strasse 4 35043 Marburg Germany

Institute of Advanced Synthesis School of Chemistry and Molecular Engineering Jiangsu National Synergetic Innovation Center for Advanced Materials Nanjing Tech University Nanjing 211816 China

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nám 2 16610 Prague Czech Republic

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