Synthesis And Catalytic Properties Of Copper Iodide Cluster Based MOFs

In recent years,Metal organic frameworks（MOFs）have gradually become a research hot with the rapid development of MOFs materials.MOFs are widely used in many catalytic fields due to their large specific surface area,high porosity,adjustable size,certain flexibility and rich structures.In this paper,two kinds of MOFs based on copper iodide[Cu_x I_y]clusters were designed and synthesized.In addition,the applications of these two MOFs in the hydroboration of alkynes and CO₂ catalytic conversion were explored in detail,respectively.The main contents of the paper are as follows:1.A new porous copper–organic framework material containing mixed valence state Cu（I）and Cu（II）blocks{[Cu^IICu₄^II₄（PMCA）₂（Py）]·NH（CH₃）₂·3DMF}（1）was synthesized by solvothermal method using ligands pyrimidine-5-carboxylic acid（HPMCA）,isonicotinic acid（HIN）,Cu（NO₃）₂ and CuI.The complex 1 was characterized by single crystal X-ray diffraction,XRD,XPS,TG,SEM,TEM and other methods.The structural measurements reveal that complex 1 is a three-dimensional network structure constructed by two types of secondary structural units,namely a binuclear[Cu₂^II（COO）₄Py₂]cluster and a tetranuclear[Cu₄^II₄]cluster.When applying 1 in the reaction of hydroboration of alkynes,it was found that complex 1 could efficiently and selectively catalyze the hydroboration of alkynes to produce the corresponding（E）-vinylboronates.Furthermore,the catalytic activity was not significantly reduced after the catalyst was recycled for five times.At the same time,complex1 also has high thermal stability and solvent stability,and exhibits highly efficient catalytic efficiency under mild reaction conditions.Additionally,this is the first example that MOF-based material can catalyze the hydroboration of alkynes with B₂Pin_2.2.Using isonicotinic acid,Dy（NO₃）₂ and CuI as raw materials,a lanthanide complex[Dy₂Cu₄I₃（IN）₇（DMF）₂]·DMF（2）based on copper iodide was synthesized by solvothermal method.Complex 2 was characterized by single crystal X-ray diffraction,XRD,TG and other methods.Structural test results show that complex 2 is a three-dimensional porous structure based on Dy one-dimensional chains and[Cu₄^II₃]clusters.Also,it shows good thermal stability and solvent stability.Catalytic results shows that the complex 2 could effectively catalyze the carboxylative cyclization of CO₂ with alkynes alcohol to generate the correspondingα-alkylidene cyclic carbonates at normal temperature and pressure,displaying a wide range of substrate adaptability.