Enantiopure FeII4L4 cages bind steroids stereoselectively

Chiral recognition underpins many biological processes, including signaling and enzymatic transformations. Mimicry of the natural systems that include these processes can provide an understanding their fundamental mechanisms enable design synthetic capable achieving similar functions. However, reported hosts only recognize small, simple chiral guests. Here, we report self-assembly a triazatruxene trialdehyde subcomponent into enantiopure FeII4L4 cages. Their chirotopic properties well-enclosed cavities cages to complex steroids through non-covalent interactions, as elucidated by X-ray crystallography. These events occur enantioselectively diastereoselectively, spanning moderate exclusive differentiation. Notably, one cage enantiomer binds equivalent canrenone, whereas other two equivalents. Microcalorimetry experiments clarify interplay enthalpy entropy during enantioselective binding.