Combining a Titanium-Organic Cage and a Hydrogen-Bonded Organic Cage for Highly Effective Third-Order Nonlinear
Yan-Ping He1,2, Guang-Hui Chen1, De-Jing Li1
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
Abstract:
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 Ti4 L6 (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 Ti4 L6 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 CH3 CN 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.
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