Combining a Titanium–Organic Cage and a Hydrogen‐Bonded Organic Cage for Highly Effective Third‐Order Nonlinear Optics.

Many metal–organic cages (MOCs) and a few hydrogen‐bonded organic cages (HOCs) have been investigated, but little is reported about cooperative self‐assembly of MOCs and HOCs. Herein, we describe an unprecedented MOC&HOC co‐crystal composed of tetrahedral Ti4L6 (L=embonate) cages and in‐situ‐generated [(NH3)4(TIPA)4] (TIPA=tris(4‐(1H‐1,2,4‐triazol‐1‐yl)phenyl)amine) cages. Chiral transfer is observed from the enantiopure Ti4L6 cage to enantiopure [(NH3)4(TIPA)4] cage. Two homochiral supramolecular frameworks with opposite handedness (PTC‐235(Δ) and PTC‐235(Λ)) are formed. Such MOC&HOC co‐crystal features high stability in water and other solvents, affording single‐crystal‐to‐single‐crystal transformation to trap CH3CN molecules and identify disordered NH4+ cations. A tablet pressing method is developed to test the third‐order nonlinear optical property of KBr‐based PTC‐235 thin film. Such a thin film exhibits an excellent optical limiting effect. [ABSTRACT FROM AUTHOR]