The Synthesis, Structures And Luminescent Properties Of 4f And D～(10) Elements Carboxylate Complexes

In this paper, the study was carried out according to the molecular fragment principle, molecular design and assembly method, energy match and transfer mechanism. Using conjugated carboxylic acids as the main ligands and phen, 2,2'-bipyridine, 4,4'-bipyridine as the secondary ligands, about 60 novel 4f, d⁰ elements carboxylate complexes are synthesized by evaporation and hydrothermal methods. These complexes are determined by IR, EA. The crystal structures and spectral properties of these complexes were determined by X-Ray single-crystal diffraction, ultraviolet absorption spectra, phosphorescence spectrum, fluorescence excitation and emission spectra. The relationship between crystal structures and luminescent properties were discussed. The main interesting results as follows: The first samples of zinc complexes with nicotinate derivatives are synthesized, and the Zn-6-OHnic complex shows a 3D supramolecular structure which constructed from strong hydrogen bonds; [Sm₃(phth)₄(phen)₂(NO₃)]_n is the first example of lanthanide coordination polymers comprising the three asymmetrical central Ln³⁺ fragments; in the structure of lanthanide 6-OHnic complexes [Tb(Onic)(OHnic)(H₂O)₅·H₂O·OHnicH]_n, there exist three types of 6-OHnicH ligands in this polymeric structure: the Onic^2- anion, the OHnic^- anion and the neutral OHnicH molecule, especially, the neutral OHnicH ligand is not coordinated to central lanthanide ions; using 2,5-piridinedicarboxylic acid as the bridging liagnd, a novel 3d-4f heterometallic complex was synthesized, an important feature of this complex, which does not occur in other MOF structures to our best knowledge, is that it possesses an unprecedented two-dimensional topology structure constructed from three-ply-like layers; [Tb₂(Dinic)₂(phen)₂(OH)₂(H₂O)₂]_n·3nH₂O forms 1D structure, and it is the first lanthanide carboxylate complex composed of OH^-bridging binuclear building unit; [Pr(fma)(OH)(bipy)·2H₂O]_n is the first sample with seven coordination number in light lanthanide ionic complexes.Lanthanide carboxylate complexes with interesting luminescent properties are synthesized. The phosphorescence spectrum of these complexes indicate that the ligands can sensitize the luminescence of lanthanide ions, however, we cannot see...