Exploiting the inherent molecular cavities of the metallosupramolecular cages, the breadth of applications in this field of research is too broad to cover comprehensively. However, chiral molecular separations (enantio-separation) employing the non-covalent interactions and functionalities of the host molecules present a formidable yet intriguing challenge. As Enantioselective separation of atropisomeric molecules, such as R/S-Binol and R/S-spirodiol, was accomplished by the Su group utilizing enantiopure Pd6(RuL3)8 (MOC-27) octahedra D-3 and L-3 (Figure ). These enantiomeric cages were produced via self-assembly of the pre-resolved chiral metalloligands (based on Ru II ) and Pd(BF4)2 and encapsulated >10 guests per cage. Extraction of these atropisomeric guests suggested a stereoselectivity of D-3 for R-isomers and L-3 for S-isomers, which ultimately led to D-3 resolving R-Binol with an ee of 34%. However, changing the inert Ru II to more labile Fe II prevented the ligand resolution before the cage preparation (Figure ). The structural analysis discloses that each cage in the absence of any chiral factor led to equal amounts of Dand L-FeL3 2+ to form FeL3 2+ racemate, which after stereoselective secondary assembly with Pd II resulted in the equivalent homochiral D8 and L8 cage (MOC-28) as racemic mixture. However, when R-Binol was present during the process of self-assembly, rapid precipitation of the reaction mixture and slow crystallization resulted in metal cages with opposite absolute stereochemistry. precipitation of the reaction mixture and slow crystallization resulted in metal cages with opposite absolute stereochemistry. As molecular recognition and separation entirely depend on the specific non-covalent interactions between the host and guest, it is rather necessary to emphasize on the specific functionalities of the ligand backbone. In 2020, the Mukherjee group reported that the presence of a chiral modifier like R-or S-Binol induced a dynamic mixture of different stereoisomers (MOC-30, Figure ) into different enantiopure octahedral cages, in a process called "reverse chiral recognition", where the handedness of the host is determined by the guest molecule. Likewise, Nitschke group emphasized on the hydrogenbonding capability of the dialdehyde component as a determining factor in the stereochemical outcome of a selfassembly into one homochiral (LL) cage, compared to the heterochiral meso component (LD) in the case of its methylated congener. Similarly, the template effect of the hydrogen bonding donor R/S-Binol or R/S-Spol induced the stereoselective self-assembly of D4or 4-type Eu4L4 cages, whereas the non-covalent confinement effect of pyrene led to a racemic mixture of enantiopure cages. Structural adaptability due to the reversibility of the coordinative bonds, 107-109 cage-in-cage complexes, can be used to confine small molecules like methane or xenon, in addition to cations and anions. In 2019, Nitschke group reported that the handedness of the tetrahedron host framework of a Fe4L4 8+ capsule (MOC-31), obtained from a triazatruxene-based subcomponent, is fixed by the enantiopure cryptophane-111 (CRY) stereochemistry, i.e., racemic mixture of PP-CRYÌD4-MOC-31 and MM-CRYÌL4-MOC-31 was formed. 111 Interestingly, prolonged heating of a mixture of MM-CRYÌL4-MOC-31 and MM-CRYÌD4-MOC-31 converted the mixture to MM-CRYÌD4-MOC-31 (Figure ), which dictates that the diastereomer interconversion involves a high energy barrier and a notable extent of cage disassembly and reassembly. Furthermore, upon the displacement of the chiral CRY by the achiral fullerene C60 within MOC-31, the pronounced cotton effect observed in the MLCT region indicates that the retention of stereochemical memory arises from the structural integrity of the complete tetrahedral framework. The interconversion between the diastereomeric forms is further pronounced for the Zn congeners of MOC-31. Based on either anticlock-or clockwise orientations of the triazatruxene moieties within the faces of MOC-31, each trischelated octahedral vertex of the tetrahedron might assume either L or D handedness. At 25°C, the distinct diastereomeric pairs (C4D4/A4L4, T1) and (A4D4/C4L4, T2) were obtained in the ratio of 66:34, which changed to 17:83 at 80°C and reversed back by cooling for 12 hours. Interestingly, the optimized structures revealed that T2 has larger pores than T1, and can house larger guests like calix [4]arene compared to the smaller guest like adamantane. Altogether, these examples show a stimulus-directed breathable system, which can be in the context of switchable catalytic systems. Notably, employing the spherical cavity of the parent cage MOC-31, and the terminal triethylene glycol functionalization enabled a reversible phase transfer strategy in D2O/CD3NO2 biphasic medium via anion metathesis, thereby enabling the purification of a broader spectrum of polyaromatic hydrocarbons. Employing the chiral auxiliary synthesis approach, by using enantiopure R/S-1-phenylethylamine or R/S-1cyclohexylethylamine afforded the enantiopure MOC-32. The arrangement of the triazatruxene moiety in this compound is dictated by the capacity of the amines to induce single handedness at the metal vertices through steric influences. Interestingly, these enantiopure hosts were found to exhibit excellent enantio-and diastereoselectivity between spironolactone (SP) and its epimer (ESP). Although they only differ in one stereogenic center, the remarkable diastereoselectivity of D4-MOC-32 and L4-MOC-32 evokes the ability to distinguish two epimers, displaying relative affinity ratios of 4.2:1 and 1:100, respectively (Figure ). Due to their highly twisted appearance, helicene-based subunits can be utilized to construct distinct coordination cages that demonstrate intriguing effects driven by chirality on their assembly. In 2018, Clever and co-workers reported the first example of a series of homochiral Pd2L4 cages (MOC-33-34), in addition to the interpenetrated Pd4L8 dimer (MOC-35), made up of eight interlocked helicenes. While rac-L 1 exclusively generates MOC-33 meso incorporating both L 1 P and L 1 M in a 1:1 ratio, rac-L 2 leads to a statistical mixture of all possible stereoisomers (PPPM/MMMP/PPMM/MMPP/PMPM/PPPP/MMMM) of MOC-34, shown in Figure . However, using enantiopure ligands, the stereochemical information of the self-assembled cages was determined by the ligand's original conformation. While the limited size of MOC-34 restricted the uptake of any 1-R-/S-camphorsulfonate anions (G1), MOC-35 showed chiral discrimination between G1 R and G1 S , along with a higher binding affinity for its diastereomeric combinations. Combination of a fluorene-backbone with emissive properties with helicene-based homochiral ligand resulted in a series of multifunctional Pd2L2L ' 2 heteroleptic cages (MOC-36) (Figure ). 118 These cages exhibit chiroptical properties that arise from the cooperative interactions between all the components. The homochiral helicene-based ligands introduce a twist to the overall structure, transmitting chiral information and leading to circularly polarized luminescence (CPL) emission from the achiral fluorene-based ligand, which is further pronounced by binding an aliphatic bis-sulfonate ligand.