Combining a Titanium-Organic Cage and a Hydrogen-Bonded Organic Cage for Highly Effective Third-Order Nonlinear Optics

作者：He, Yan-Ping; Chen, Guang-Hui; Li, De-Jing; Li, Qiao-Hong; Zhang, Lei; Zhang, Jian^*

来源：Angewandte Chemie - International Edition, 2021, 60(6): 2920-2923.

DOI：10.1002/anie.202013977

• metal-organic cages
• nonlinear optics
• self-assembly
• titanium

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(Delta) and PTC-235(Lambda)) 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.

• 单位
  中国科学院大学; 结构化学国家重点实验室; 中国科学院福建物质结构研究所