Syntheses, Structures, And Properties Of A Series Of Coordination Polymers With Carboxylate And N-Heterocyclic Ligands

In this article, we introduced the concepts, synthesis, structure types and applications of coordination polymers. We prepared six new ligands containing N-doner and successfully synthesis sixteen unreported metal-organic polymers. All these complexes were characterized by infra-red spectrum (FT-IR), elemental analysis and X-ray crystallography diffraction analysis to elucidate their structures both in solution and in solid state. We also investigated the thermal stabilities and the photoluminescent properties of some complexes in solid state. The paper contained the following works:1. We used1,10-phenanthroline to synthesis six liands containing N-doner, namely ipdt, dipt, mip, ipm, cipt and dnpt, which were characterized by FT-IR.2. We used liand containing N-doner and carboxylic acid to coordinate transition metals to synthesis ten coordination polymers successfully, namely{[Zn2(ipdt)2(BDC)2(H2O)]·3H2O}n (1),{[Mn(dipt)(m-BDC)3]n (2),{[Mn(dipt)(BDC)-H2O]n (3),{[Mn(dipt)2(n-BDC)2]n (4),[Cd2(mip)2(BDC)2]n (5),[Cd2(mip)2(1,8-NDC)2]·H2O (6), Cd(mip)2(NTC)2(7),[Cdi.s(mip)(GTC)]n (8),[Cd(mip)(1,4-NDC)]n (9) and [Cd(ipm)(1,4-NDC)]n (10). The transition metals were Mn2+, Zn2+and Cd2+ions. All these complexes were characterized by elemental analysis, IR, X-ray crystallography diffraction and thermogravimetric analyses (TGA). The luminescent properties for some complexes are also discussed in detail. Complexes1-5were one-dimensional (1D) chain structures. Complexes6,7were0D structures, and the hydrogen bonds between adjacent molecules lead the0D to1D or2D supramolecular structures. Complexes8-10were2D layer structures. The C-H…O hydrogen bonds and C-H…π stacking played an important role in the building of higher dimensional frameworks. Compared with the similar complexes, complexes1-10exhibit good thermal stability, which proves that the existences of H-bonds favor the build of supramolecular structure and reinforce the stability of complexes.3. Six coordination polymers had been synthesized by the liands containing N-doner and carboxylic acid to coordinate Pb2+ions:{[Pb2(mip)2(BDC)2]·H2O}n(11),{[Pb2(cipt)2(BDC)2]·2H2O}n (12),[Pb(cipt)(1,4-NDC)]n (13),[Pb(mip)(1,4-NDC)]n (14),[Pb(dnpt)(BDC)2]n (15) and [Pb(ipm)(BDC)3]n (16). All these complexes were characterized by elemental analysis, IR, X-ray crystallography diffraction and thermogravimetric analyses (TGA). The luminescent properties for some complexes are also discussed in detail. Complexes11-15were1D structure. Complex16was2D butterfly wings structure. From the TG curves, we can prove that the existences of H-bonds favor the build of supramolecular structure and reinforce the stability of complexes.