To confirm the chiral skeleton of these CCMs, their single crystals were grown via slow diffusion of Methanol into their solution in tetrahydrofuran (THF). Fortunately, crystals suitable for single crystal analysis had been obtained for RBT-OMe and SBT-OMe (Figure and, CCDC 2408898 for RBT-OMe and CCDC 2408900 for SBT-OMe, Table ). As indicated, the distance between two C=C bond of TAE unit was estimated to be 10.3 Å , whereas the distance between the chiral axis in BINOL moiety was measured to be about 8.3 Å . Notably, the TAE unit within the cyclic skeleton of RBT-OMe had adapted the P-helicity, whereas their counterparts SBT-OMe displayed M-helicity with anticlockwise torsion in TAE core. The chiral transfer between BINOL tethers to TAE units had paved the basis for efficient and precise synthesis toward CCMs. The dihedral angle between naphthalene rings within the macrocycle was recorded to be 79° and 97° (Figure ), whereas the dihedral angle observed in the crystals of S-BINOL (CCDC 761065) or R-BINOL (CCDC 761061) was 76.6°. This increased angle directly supported the increased strain within the π-conjugated cyclic skeleton, which driven BINOL moiety far from its pristine structure. Meanwhile, the dihedral angles between naphthalene ring of BINOL with C=C bond in TAE unit were also obviously smaller than the angles between peripheral aryl rings and ethylene linkage (Figure ). This smaller angle within the cyclic skeleton was also attributed to the constraint from the congested conjugated macrocycles.