Construction And Properties Study Of Organic Frameworks Based On Porphyrin

Within the last two decades,interest in the field of porous materials has grown tremendously because of their outstanding performance and broad applications for uses such as in gas storage,gas separation,superhydrophobic interfaces,catalysis,energy conversion,energy storage,and optoelectronics et al.Chemists have found ways to prepare a wide variety of porous materials;however,it had been proven difficult to synthesize organic polymer networks with discrete pores until the concept of reticular chemistry,which uses topologically designed building blocks,was proposed to construct these porous materials.Metal-organic frameworks(MOFs)were the first porous materials to be synthesized using reticular chemistry;Covalent organic frameworks(COFs)were another crystalline porous materials constructed by integrating organic building blocks into periodic topological structures.Porphyrins are macrocyclic compounds,composed of four conjugated pyrrole connected by methylene,possessing structural stability and diverse functions,and exhibiting optical,electric,and magnetic properties,probably leading to.the supramolecular assembly of porphyrins wtih these excellent properties.Therefore,the porphyrin-based porous materials maybe have different potential fields in life,information,material science.Herein,a series of porphyrin-base COFs/MOFs were constructed from porphyrins and organic building block or metals node.Meanwhile,we also studied their application in catalysis and dye adsorption,the specific contents as following:1 Metal free 5,10,15.20-tetra(p-amino-phenyl)porphyrin(H2TAPP)with additional nitrogen atoms at the tetrapyrrole periphery was employed to construct a nitrogen-rich covalent organic framework(H2P-Bph-COF)with the help of'4.4'-biphenyldialdehyde under solvothermal condition.The abundant and periodically distributed N atoms in H2P-Bph-COF stabilize and uniformly disperse the Pd ions inside the COF structure,resulting in a remarkable catalytic activity towards the Suzuki-coupling reaction between bromoarenes and arylboronic acids under mild condition with high yields of 97.1-98.5%.The present result appears to extend the catalysis application of porphyrin-based COFs from radical or carbene participated oxidation reactions into the Suzuki-coupling reaction.2 A novel imine-linked porphyrin covalent organic framework(COF)CuP-DMNDA-COF with a large surface area was constructed from the condensation between 5,10,15,20-tetra(p-amino-phenyl)porphyrinatocopper(II)(CuTAPP)and 2,6-dimethoxynaphthalene-1,5-dicarbaldehyde(DMNDA)under solvothermal condition.Simple treatment of CuP-DMNDA-COF with iron(III)in acetone led to the formation of Fe-coordinated COF material CuP-DMNDA-COF/Fe,which exhibits superior adsorption performance for Rhodamine B(RhB)with easy recyclability and sustainability,indicating its good application potential for wastewater treatment.3 A series of four porphyrin-alkaline earth metal-organic frameworks[Mg(HDCPP)2(DMF)2]n·(H20)7n(1),[Ca(HDCPP)2(H20)2]n(DMF)1.5n(2),[Sr(DCPP)(H20)(DMA)]n(3),and[Ba(DCPP)(H20)(DMA)]n(4)was isolated for the first time from solvothermal reaction between metal-free5,15-di(4-carboxyphenyl)porphyrin(H2DCPP)and alkaline earth ions.Single-crystal X-ray diffraction analysis reveals the 2D and 3D supramolecular network with periodic nanosized porosity for 1-4,respectively,The whole series of MOFs,in particular,compounds 1 and 2 with intrinsic low molecular formula weight,exhibit superior adsorption performance for methylene blue(MB)with excellent capture capacity as represented by the thus far highest adsorption amount of 952 mg g-1 for 2 and good selectivity,opening a new way for the potential application of the main group metal-based MOFs.