The Synthesis And Post-functionalization Of The MOFs Based On Disubstituted Ligands Of4,4’-biphenyldicarboxylic Acid

Metal-organic open frameworks (MOFs) are the best candidates for modification with functionalities on their organic linkers. Post-functionalization of the thermal stable MOFs on their organic moities is gradually becoming prevalent in targeting their potential applications in molecular separation and catalysis. This dissertation focuses on the post-functionalization of the iso-reticular MOFs of IRMOF-9,-10, and MOF-602, which includes following three parts:1. Functionalization of the ligands of4,4’-biphenyldicarboxylic acid: the ligands of2,2’-dinitro-4,4’-biphenyldicarboxylic acid (HL1),2,2’-diamino-4,4’-biphenyldicarboxylic acid (HL2) were synthesized. Fortunately, an unprecedented organic compound1,6-dihydro-1,6-pyroline-3,8-dicarboxylic acid (HL3), which can be used as a ligand for MOF construction was also accidently obtained.2. Synthesis and characterization of the iso-reticular MOFs of IRMOF-9,-10, and MOF-602, based on the ligands of HL1’3with double number of nitro-and amino-groups:[Zn4O(L1)3-H2O]n (1)(with the framework of IRMOF-9),[Cu2(L1)2-(DMA)2(H20)o.5]n (2),[Cu2(L1)2-(H2O)2]n (3),[Cu2(L1)2·(DMSO)o.8(H20)1.7]n (4)(with the framework of MOF-602) and [Zn4O(L2)3-(H2O)12]n (5)(with the framework of IRMOF-10).3. Post-functionalization of the MOF of [Zn4O(L2)3·(H2O)12]n (5) with (R)-(-)-epichlorohydrin and2-bromonicotinaldehyde+Co(II):the functionalized MOFs of (Zn4O)[L-(NC3H5OC1)22]3(5a) and (Zn4O)[L-(NCPyCoC12)22]3(5b) were obtained.