Selective Encapsulation and Chiral Induction of C 60 and C 70 Fullerenes by Axially Chiral Porous Aromatic Cages

Chiral induction has been an important topic in chemistry, not only for its relevance in understanding the mysterious phenomenon of spontaneous symmetry breaking in nature but also due to its critical implications in medicine and the chiral industry. The induced chirality of fullerenes by host–guest interactions has been rarely reported, mainly attributed to their chiral resistance from high symmetry and challenges in their accessibility. Herein, we report two new pairs of chiral porous aromatic cages (PAC), R‐ PAC‐2 , S‐ PAC‐2 (with Br substituents) and R‐ PAC‐3 , S‐ PAC‐3 (with CH 3 substituents) enantiomers. PAC‐2 , rather than PAC‐3 , achieves fullerene encapsulation and selective binding of C 70 over C 60 in fullerene carbon soot. More significantly, the occurrence of chiral induction between R‐ PAC‐2 , S‐ PAC‐2 and fullerenes is confirmed by single‐crystal X‐ray diffraction and the intense CD signal within the absorption region of fullerenes. DFT calculations reveal the contribution of electrostatic effects originating from face‐to‐face arene‐fullerene interactions dominate C 70 selectivity and elucidate the substituent effect on fullerene encapsulation. The disturbance from the differential interactions between fullerene and surrounding chiral cages on the intrinsic highly symmetric electronic structure of fullerene could be the primary reason accounting for the induced chirality of fullerene.