ABSTRACT The design and synthesis of fullerene‐based supramolecules are of great scientific significance. In the present work, the planar pentacoordinate carbon skeleton CBe 5 has been embedded into C 50 ( D 5h ) ( 1 ) to construct the supramolecular complex CBe 5 @ 1 , however, this embedding increases the steric hindrance between 1 and CBe 5 (the configuration of CBe 5 changed to be pentagonal pyramid). Inspired by the 2004 synthesis of 1‐ Cl 10 ( Science 2004 , 304 , 699), where ten Cl atoms effectively passivated the reactive sites of 1 , the novel supramolecular complex CBe 5 @ 1‐ Cl 10 with the planar pentacoordinate carbon skeleton CBe 5 was successfully designed. Further, the adaptive natural density partitioning (AdNDP) analysis shows that the presence of Cl 10 expands the range of electron delocalization and forms five 5c‐2e σ ‐bonds between 1 and Be. Subsequently, we employed the energy decomposition to find that charge interaction and polarization dominate the intermolecular forces in both CBe 5 @ 1 and CBe 5 @ 1‐ Cl 10 , the overlap degree of the electron cloud is relatively high, and the spatial steric obstruction causes a strong repulsion in CBe 5 @ 1 , however, with external Cl substitution, electrostatic and polarization effects are weakened while electron delocalization is enhanced for CBe 5 @ 1‐ Cl 10 . Furthermore, the incorporation of Cl 10 also results in notable alterations in the charge distribution and aromaticity of the system. And infrared and UV–vis spectrums can be used by the experimentalists to identify this novel saucer‐shape supramolecular complex CBe 5 @ 1‐ Cl 10 . It is hoped that this work will open up a brand‐new path for the structural innovation and application of supramolecular materials.
Liu et al. (Fri,) studied this question.