Synthesis, Structures And Magnetic, Fluorescent Properties Of Coordination Polymers Based On2,2’-(Hydroxyphosphoryl) Dibenzoic Acid

In the design of the crystal structure, semi-rigid ligand has incomparable advantages. At present, aromatic carboxylic acid ligands whose centeratom is C, O, S, N and so on, has potential applications in many fieldssuch as magnetic and fluorescent, catalysis, ferroelectric, nonlinear optical(NLO) property. In this paper, we design and synthetize the main ligand2,2’-(hydroxyphosphoryl)dibenzoic acid with P atom, and choose some secondary ligand contained N atoms, build a series of novel configurable coordination polymers, determine their crystal structure, and also test some polymers magnetic, fluorescent properties.1) We had synthesized6coordination polymers1~6whose central metalions is Co2+. In this system, different ligand contained N atoms wereadded into as secondary ligands, finally we got five compounds1-5.Compound3is three-dimensional structure with Co5cluster subunit, behave spin-glass feature in magnetism field. Compound6features a1Darchitecture constructed of ten nuclear clusters, shows a weakly ferromagnetic state caused by spin-canting.2)2,2’-(hydroxyphosphoryl)dibenzoic acid was chosen as a principal ligand, Zn2+, Cd2+, Mn2+, Ag+is the coordinated metal ions, sometimes secondary ligands with N atoms enter for the reaction, finally9coordination polymers7~15were obtained. For some coordination polymers with the same metal ions, when add into or change secondary ligands, the structure of crystal is differen. Alternatively,we can obtain different structure of crystal only by change the metal ions. The fluorescence mechanism of Compound7-13should be ligand-based luminescence, therange of emitted light is in346-383nm. We got componds14and1 5by adjust the molar ratio of reactant, and got a conclusion that thebest molar ratio of reactant is3:1and9:1according to the PXRD patterns. The emit light of two kinds of compound is508,496nm respectively, the fluorescence mechanism is ligand-to-metal charge transfer(LMCT).3) We built a series of3d-4f metal organic coordination polymers16~20by using rare earth ions (Gd, Dy)and transition metal ions (Co, Ni, Mn). In the process of crystal formation, because of the bigger ionic radius of rare earth ions, the characteristic of crystal structure is that rareearth ion is in the center, and transition metal ions surround that rareearth ion. Compounds16,17,19have the same constitutional unit, but form0D,1D,3D structure respectively for the influence of the secondary ligands.4) Compound21was synthesized by the reaction of copper ions and primary ligand. This coordination polymer features1D ladder-shape structure, monoclinic crystallographic system, acentric point group, slightly soluble to water, with the property catalyzing the reaction between H2O2and morin.