Synthesis, Structure And Properties Of New Coordination Polymers Constructed By Flexible Aromatic Carboxylic Acid

The design and construction of new functional coordination polymers have been one of the most intensive research topic in coordination chemistry,supramolecular chemistry and crystal engineering due to their novel topological structures and potential applications in the optical,electrical,magnetism,molecular recognition and catalytic fields.The dissertation is aimed to synthesize luminescent coordination polymers by the reaction of d¹⁰ metal ions or strong luminescent rare earth ions with three kinds of flexible aromatic carboxylic acids. Four series,24 d¹⁰ transition/lanthanide coordination polymers are designed and constructed. All coordination polymers are characterized by elemental analyses,IR spectra,X-ray single crystal diffraction,thermal gravimetric analyses,and luminescence analyses.This dissertation includes the following five chapters:(1) The Chapter 1:Preface.The concepts and principles of coordination chemistry, supramolecular chemistry and crystal engineering are simply introduced.Reviews on the sorts of coordination polymers and the research development of complexes containing of the muti-pyridine,aromatic carboxylic acid and pyridine-carboxylic acid related with this dissertation were also briefly depicted.(2) The Chapter 2:Eight novel d¹⁰ transition/lanthanide metal coordination polymers based on 4,4'-sulfonyldibenzoic acid(H₂sfdb) and auxiliary ligands containing N have been synthesized successfully.Complexes 1-7 show different 1D chains,such as zigzag chains (1-3),square-wave-like chains(4,5),grid chain(6),double chain(7).Complex 8 is 2D network structure,which is also the first lanthanide metal coordination polymers based on H₂sfdb ligand.The influence of the metal ions,auxiliary ligands containing N and reaction conditions effect on the structure of compounds.In a comparison of the structures of 1 and 5-7,it was found that the final structure can be tuned by the influence of ligands containing N on carboxyl coordination modes,while the structures of 2,3,4 can be mostly tuned by metal/ligand ratios.Compound 8 has strong luminescent intensity and longer luminescent lifetime,which can be used as potential green fluorescence materials.(3) The Chapter 3:Four d¹⁰ transition metal coordination polymers 9-12 and four lanthanide metal coordination polymers 13-16 based on 4,4'-oxydiphthalie acid(H₄odpa) and auxiliary ligands containing N have been synthesized successfully.We firstly found that decarboxylation of a single carboxyl group from H₄odpa ligand involving Ag(I),which provides some useful information on study the mechanism of decarboxylation.Compounds 13-16 are all 2D bilayer network structures,which are also the first example of lanthanide metal coordination polymers based on odpa ligand.Compounds 13 and 14 can be used as potential red and green fluorescence materials.(4) The Chapter 4:We have hydrothermally synthesized three novel heterobimetallic coordination polymers(17-19) based on odpa ligand and d¹⁰ transition metal and main group metal.Compounds 17 and 18 are unprecedented 2D bilayer networks.Compound 19 presents a 3D coordination polymer based on both polynuclear heterobimetallic clusters.Interestingly, the novel 2D Na-O or Cd-Na polymeric networks are inserted in the anion networks.(5) The Chapter 5:Five d¹⁰ transition metal coordination polymers 20-24 based on 4,4'-(hexafluoroisopropylidene)diphthalic anhydride(hfpd) and auxiliary ligands containing N mixed ligands have been synthesized successfully.Our studies show that the structure features of the auxiliary ligands containing N(size,shape,flexibility) and metal ions have significant effect on the formation,structures and properties of the resulting compounds.The successful synthesis of these compounds may provide some useful information on synthesize new compounds based on hfpd ligand.