Synthesis, Structures And Luminescent Properties Of Metal-Organic Frameworks Based On TCOPM Ligand

In recent years, carboxylic acid coordination polymers are widely used in the construction of metal-organic frameworks(MOFs, metal-organic coordination polymers), due to their rich coordination modes and strong coordination ability. In this paper, Tris(p-acetyphenyl) methane(TAc PM) was synthesized via two steps that triphenylmethane(TPM) was used as the starting material. The structures of the products was characterized by FT-IR and 1H-NMR. Then, twelve new coordination polymers were synthesized by using TCOPM, N-donor ligands and transition metal ion(Zn2+、Cd2+、Co2+) through the solvothermal reactions. These complexes were characterized by single-crystal X-ray diffraction, IR and power X-ray diffraction,the thermal stability was studied by thermal-gravity analysis. In addition, the luminescent properties in the solid state of Zn(II) and Cd(II) complexes were also investigated.The main results are as follows:1. Tris(p-acetyphenyl) methane(TAc PM) was synthesized via the Friedel-Crafts reaction of triphenylmethane(TPM) as the starting material. TAc PM was synthesized to obtain triphenylmethane-4,4’,4’’-tricarboxylic acid(TCOPM)through the bromoform reaction. The structures of the products were characterized by FT-IR and 1H-NMR.2. Five new coordination polymers Zn3(TCOPM)2(OH)]·C2H7Nn(1),Zn2(TCOPM)(2,2’-bipy)(OH)·1.25DMF(2), Zn2(αOH-TCOPM)(phen)(OH)·DMF(αOH-TCOPM=tris(p-carboxyphenyl)methanol)(3),Zn2(αOH-TCOPM)(tpy)(OH)(H2O)(4) and Zn3(αOH-TCOPM)2(dpe)·2H2O(5) were synthesized by using TCOPM,Zn(NO3)2·6H2O and N-donor ligands(2,2’-bipyridine; 1,10-phenanthroline;2,2’:6’,2’’-terpyridine; 4,4’-vinylenedipyridine) through the solvothermal reaction.X-ray crystallography analysis reveals that 1 and 5 exhibit 3D open frameworks,while 2-4 possess 2D layered structures. IR spectra of 2-5 all exhibit the typical peak of carboxyl group. Furthermore, the emission bands of these complexes are similar to that of the free TCOPM and the maximum values of emission show blue shifts.3. Four new coordination polymers Cd3(TCOPM)2(DMF)2(H2O)2(6),Cd3(TCOPM)2(4,4’-bipy)(7),Cd3(TCOPM)2(dpe)(8)and Cd3(αOH-TCOPM)2(2,2’-bipy)2·2DMF(9) were synthesized by using TCOPM, Cd(NO3)2·6H2O and N-donor ligands(2,2’-bipyridine; 4,4’-bipyridine; 4,4’-vinylenedipyridine) through the solvothermalreactions. X-ray crystallography analysis reveals that 6 and 9 exhibit 3D open framework, while 7-8 possess a 2D layered structure. IR spectra of 6-9 all exhibit the typical peak of carboxyl group. Furthermore, the emission bands of these complexes are similar to that of the free TCOPM and the maximum values of emission show blue shifts.4. There new coordination polymer Co2(αOH-TCOPM)(OH)(H2O)4·DMF(10),Co3(αOH-TCOPM)2(4,4’-bipy)3(H2O)6·2H2O(11),Co3(αOH-TCOPM)2(dpe)3(H2O)6·H2O(12) were synthesized by using TCOPM, Co(NO3)2·6H2O and N-donor ligands(2,2’-bipyridine; 4,4’-bipyridine; 4,4’-vinylenedipyridine) through the solvothermal reactions. X-ray crystallography analysis reveals that 10 exhibit a quadrilateral 2D layered structure, while 11 and 12 exhibits an extraordinary 2D interpenetrating layered structure. IR spectra of 10-12 all exhibit the typical peak of carboxyl group and have no luminescent properties.