Synthesis, Characterization And Performance Study Of Metal Organic Framework Compounds Based On Nitrogen-containing Heterocyclic Ligands

The quickly developed metal-organic frameworks(MOFs)have great application potentials in various fields.MOFs constructed from mixed-ligands often present water and thermal stability.In this paper,solvothermal/hydrothemal synthesis method were used and the main contents of this paper are listed as follows:(1)1-(3,5-bis((1H-1,2,4-triazol-1-yl)methyl)-2,4,6-trimethylbenzyl)-1H-1,2,4-triazo-le(tttmb)and 1,3,5-benzenetricarboxylic acid or 1,3-benzenedicarboxylic acid were applied as mixed-ligands,and two new MOFs[Cu(tttmb)(HBTC)]·1.5H2O(1)and[Cu2(tttmb)2(m-HBDC)Cl2]·6H2O(2)have obtained.We have also discussed the effect of different synthetic conditions on the final products.Compound 1 and 2 exhibit characteristic fluorescence properties,and are wide band-gap semiconductors.In addition,We used post-synthezied method to study the hydro-thermal reaction of[Cu11(tttmb)2Cl11(H2O)3](3),[Cu7(tttmb)2Br4C13]·3H2O(4)and[Cu7(tttmb)2Br7-H2O](5)with H3BTC.As a result,partial conversion of 4 to[Cu3(tttmb)2Br606-H2O](6)was observed.Compound 4 and 5 exhibted chemical stablity for 3 days in the aqueous soolution of 120℃.This conclusion provide support of syntheses of more potentially highly stable MOFs based on CuBr and CuI clusters as sub-building units.(2)[Cu3(Py)6(BTC)(μ3-NO3)Cl2]·2H2O(7)and[Cu3(Py)9(BTC)2]·8H2O(8)were synthesized by copper chloride and ligands but different solvents(H2O/ethanol/N,N’-dimethylformamide)from that of compound 1.The adsorption properties of compound 8 had been discussed.Compound 7 and 8 were assembled from Cu(II)with H3BTC and pyridine without tttmb.It shows that solvents played important roles in the building of MOFs.It provides a new method for the synthesis of MOFs.(3)Porphyrin and metallopophyrin with unique photoelecric properties have been used as chromogenic agents,spectral materials,molecular recognition and probe materials.We have got the crystals of meso-tetra(4-imidazoyl)porphyrin(9)and copper(Ⅱ)-TImP(10).Compound 10 exhibits characteristic fluorescence properties,and is a wide band-gap semiconductor.The results will help us understand and purify TImP,in addition,these findings will facilitate further study of TImP and obtain more porphyrinic MOFs based on TImP.