The Construction And Catalytic Properties Study Of Copper (Cluster)-based Metal-Organic Frameworks

C-N bond widely exists in a variety of medicines,pesticides and natural products with biological activity,and it is an important part of many chemical materials.One of the most effective methods to form aryl C-N bond is Ullmann type coupling.As a non-noble metal catalyst,copper is often used to catalyze Ullmann C-N coupling reactions.What's more,copper is cheap and easy to obtain and also has low toxicity properties.Asymmetric Ullmann coupling faces great challenges in the design of chiral ligands and reactions,so the study of these reactions is of great significance.Metal-organic Frameworks(MOFs)are a kind of unique porous crystalline materials composed of metal ions/clusters and organic ligands.Their structural diversity,functional flexibility and high surface area make them widely be used in the fields of gas adsorption,gas separation and heterogeneous catalysis.Functional MOFs can be constructed by adjusting the types of metal centers,organic ligands and guest molecules.Based on this,two novel functional MOFs were constructed in this paper.One of the two has a unique chiral structure and can be used as chiral catalyst to catalyze intramolecular asymmetric Ullmann C-N coupling reactions.(1)The ligands DPNDI and PTZ were designed and synthesized with 1,4,5,8-naphthalene tetraformyldiimide and phenothiazine.The ligands were coordinated with copper to construct Cu-DPNDI and Cu-PTZ.Their nodes respectively are copper and copper sulfur clusters.These two MOFs have not only novel structures,but also good thermal stability.They have good photophysical activity.The analysis of single crystal structure shows that Cu-PTZ provides sufficient pore size,which is conducive to catalytic reaction.(2)Cu-PTZ-1 and Cu-PTZ-2 with relatively single configurations were obtained by chiral resolution.Cu-PTZ-2 was used to catalyze the intramolecular asymmetric Ullmann C-N coupling reaction,which realized the control of the product configuration to some extent.This material provides a new idea for the development of new asymmetric C-N coupling reaction catalysts.