High Chemical Reactivity Studies Of Metal-Organic Frameworks Under Vapor Assisted Aging And Synthesis Of Some Imine Porous Organic Polymers

Metal-organic frameworks and porous organic polymer have attracted intensive interest from researchers with diverse expertise in recent years. Not only do they have structural controllability, large specific surface area, but also have potential application in catalysis, selective adsorption and separation, gas storage and drug delivery.In this paper, origanic carboxylic acids and metal oxides were selected for structural transformation and interconversions under vapor-assisted aging. Four organic carboxylic acids, namely, ftumaric acid (H2fum), 1,4-benzenedicarboxylic acid (H2bdc), isonicotinic acid (Hina) and nicotinic acid (Hna) were chosen to react with zinc or cadmium oxide and added NH4Cl (5 wt %) and H2O, DMF, or MeOH (100 ?L) to obtain 13 metal-carboxylate frameworks: [Zn(fum)(H2O)4](1,1D),[Zn(fum)(H2O)2](2,2D), [Zn(fum)](3, 3D),[Zn2(fum)2(bipy)](4),[Zn(bdc)(H2O)2](5,1D), [Zn(bdc)(H2O)]·DMF(6, 2D),[Zn(bdc)(H20)](7,3D),[Zn(ina)2(H2O)4](8,0D),[Zn(ina)2](9,3D),[Cd(ina)2(H2O)4](10,0D),[Cd(ina)2(H20)]·DMF(11,3D),[Zn(na)2(H20)4](12, 0D),[Zn(na)2](13, 2D). We used H2O, DMF, and MeOH in four series of structural interconversions and transformations of MOFs under VAG. In the H2O VAG-driven rehydration reactions, that is,6 ?5, 7 ?5, 9 ?8,11?10, and 13 ?12, the water vapor provided water molecules as ligands. The DMF vapor served as a template in reactions 1 ?4, 5 ?6, 7 ? 6, and 10 ?11, and the DMF molecules are present in the pores of 6 and 11 as guest ecules. MeOH vapor usually led to dehydration reactions, namely, 1 ? 2, 2 ? 3, 1 ? 3, 6? 7, 8 ? 9,and 12?13. However, MeOH is neither a reactant nor a template in these reactions.Under the condition of DMF, MeOH or H2O steam aging conditions, the 1D, 2D and 3D structures can be transformed into each other at room temperature, which indicates that the obtained MOFs have high chemical reactiving activity. In addition, the products 1, 2, 3 can react with bipy at room temperature under DMF vapor aging to obtain a pillared MOFs.1,3,5-Triformylphloroglucinol was chosen to react with tris (2-aminoethyl) amine,m-phenylenediamine, 4,4'-diaminodiphenylmethane, 9,9-bis (4-aminophenyl)fluorene,4,4'-diphenylamine diphenyl ether, pararosaniline base,4,4'-diaminobiphenyl-2,2'-disulfonic acid to get 7 different porous organic polymer. All porous organic polymer have very high thermal stability and show very good chemical stability in organic solvent for 7 days, and porous organic polymer 7 can be dissolved in water and a few layers structure is obtained.