Designed Synthesis And Application Of Organic Cage Materials

Organic molecular cage is a kind of three-dimensional organic molecule with definite geometric structure and molecular cavity,which plays an important role in supramolecular chemistry research.In recent years,it has been found that organic molecular cages can not only be used as a new type of porous materials,but also as structural units to construct porous materials.Due to its unique cavity structure,molecular cage based porous materials exhibit excellent properties in host and guest chemistry,gas adsorption and separation,catalysis and so on,which is a frontier research topic in the field of structural organic chemistry,supramolecular chemistry and materials science.In this paper,the applications of molecular cages in stabilizing ultrafine metal nanoparticles and constructing organic porous polymers are studied.The main research contents include:（1）Three organic molecular cages（OMC 1-3）with different functional group structures（imines,secondary amines and tertiary amines）were designed and synthesized,and used as templates for the controlled synthesis of ultrafine Pd nanoparticles.Three kinds of Pd@OMC complexes were obtained,in which the Pd NPs size of tertiary amine-stabilized metal nanocomposite（Pd@OMC-3）was 1.78 nm,which was smaller than that of imine-stabilized Pd NPs（2.41 nm）and secondary amine-stabilized Pd NPs（2.58 nm）.Compared with Pd@OMC-1 and Pd@OMC-2,Pd@OMC-3 exhibited better catalytic activity in the catalytic Suzuki-Miyaura coupling reaction.This work represents the first controllable synthesis of superfine metal nanoparticles using tertiary amine molecular cage as stabilizer,which provides a new approach for the design and synthesis of efficient and stable metal nanocatalysts.（2）Two molecular cages with different cavity sizes（Cage 1 and Cage 2）were designed and synthesized.Using Cage 1 and Cage 2 as new monomers,Cage-POP-1 and Cage-POP-2 were prepared by free radical polymerization.The structures of organic polymers were fully characterized by solid state nuclear magnetic,infrared spectroscopy and et al.The abundant content of N element and the structure of molecular cage cavity in Cage-POPs give them excellent adsorption properties toward iodine and carbon dioxide.Comparative experiments show that Cage-POP-1 has higher adsorption capacity of iodine and carbon dioxide than Cage-POP-2.It is worth mentioning that the adsorption rate of Cage-POP-1 for iodine in water is 21.4 g g^-1min^-1,which is superior to all reported porous materials.This work represents the first example to investigate the relationship between the size of the intrinsic cavity of molecular cage and the structure activity of materials,which provides a new idea for the design and synthesis of related materials in the future.