RE - Carboxylic Acid And Lead With 3-fluoro-phthalate With The Structure And Luminescence Material

Sixteen complexes were obtained by hydrothermal method with3-sulfobenzoate (3-SBA),4-sulfobenzoate (4-SBA) and3-fluorophthalate (H2Fpht) as the first ligand, the N-donor ligands (IP=H-imidazo[4,5-f][1,10]-phenanthroline,4-PDIP2-(4-pyridine)imidazo[4,5-f][1,10]-phenanthroline, bpy=2,2’-bipyridine) as the auxiliary ligand. The structures, composition and properties were characterized through IR spectrometry, X-ray single-crystal diffraction, elemental analysis, fluorescence spectrometry and DTA-TGA. The following are the main results:1.3-sulfobenzoate as the first ligand,1H-imidazo[4,5-f][1,10]-phenanthroline as the auxiliary ligand, and four new lanthanide complexes were prepared by hydrothermal method:{[Ln(3-SBA)(IP)OH(H2O)]H2O}n (Ln=Gd1, Eu2and Tb3),{[Pr2(3-SBA)2(IP)2(NO3)2(H2O)2]·H2O}n (4)(3-SBA=3-sulfobenzoate, IP=1H-imidazo[4,5-f][1,10]-phenanthroline). The complexes1-3are isomorphous with similar crystal structures. Complexes1-3feature ID chain structure constructed from {LnO6N2} units,3-SBA and OH ligands, the chains are linked by hydrogen bonds and π-π interactions to give a3D supramolecular structure. Complex4shows a ID double helix which is built from {LnO7N2} units and3-SBA linkers, the3D architecture of4is formed by C-H…O noncovalent interaction. In addition, the complex1shows a large broad emission band in the400-580nm region (blue-green). Complex2emits red fluorescence, the fluorescence lifetime is0.285±0.005ms and the quantum yield is11.26%. Complex3emits green fluorescence, the fluorescence lifetime is0.287±0.002ms and the quantum yield is9.28%. The White-light emission was realized based on the doping concentration of the Eu(III) ion in the Gd(III) complex for the first time by varying the excitation wavelength.2. Reactions of rare earth metals with4-sulfobenzoate and1H-imidazo[4,5-f][1,10]-phenanthroline afforded a series of lanthanide complexes,{[Ln(4-SBA)(IP)(OH)]·1.5H2O}n (Ln=Sm5, Eu6, Gd7and Tb8)(4-SBA=4-sulfobenzoate, IP=1H-imidazo[4,5-f][1,10]-phenanthroline). Complexes5-8are isostructural, the {LnO6N2} units are connected by sulfonate groups and4-SBA ligands to generate a2D layer structure, the layers are stacked via N-H…O hydrogen bonds resulting in a3D network. The weak metal-centered luminescence of Sm(III) and intense ligand-centered lumicescence were observed in5. Complex6and8emit red and green fluorescence, respectively. Complex7produces a large broad emission in the green spectral region (410-580nm), which can be assigned to the ligand-centered luminescence. White light emission of doped complex was realized by Sm(III) as matrix for the first time.3.3-sulfobenzoate as the first ligand,2-(4-pyridine)imidazo[4,5-f][1,10]-phenanthroline as the auxiliary ligand, and three new lanthanide complexes were prepared by hydrothermal method:[Ln2(3-SBA)2(4-PDIP)2(OH)2(H2O)4]·2H2O (Ln=Sm9, Eu10, Gd11)(3-SBA=3-sulfobenzoate,4-PDIP=2-(4-pyridine)imidazo[4,5-f][1,10]-phenanthroline). Complexes9-11are binuclear molecular which are connected by hydrogen bonds to generate3D network. The fluorescence of9and11come from the ligands. Complex10displays the characterstic emission of Eu(III) ion.4.3-fluorophthalate (H2Fpht) was chosen as the first ligand and2,2’-bipyridine (bpy) as the auxiliary ligand to react with lead ions under hydrothermal method and five new complexes were obtained:{[Pb2(Fpht)2(bpy)(H2O)2]·2H2O}n (12&13),[Pb(Fba)(bpy)(NO3)]n (14),[Pb4O2(Fba)4]n (15) and [Pb5(Fpht)4(Fba)2]n (16)(Fpht=3-fluorophthalate, Fba=3-fluorobenzote, bpy=2,2’-bipyridine).3-fluorobenzote was obtained from the decarboxylation reaction of3-fluorophthalate. Interestingly, the decarboxylation reaction was observed in complexes14,15and16. Complexes12and13contain tetranuclear clusters [Pb2(COO)4]2and Fpht ligands as linkages to assemble the ID chain structure, ID chains are connected to2D network structure through "ternary water clusters" hydrogen bonds and further extended into a final3D supramolecular via O-H-F hydrogen bonds. Complexes14and15possess ID chain structure, and14possesses double helical chains. The3D supramolecular frameworks of complexes14and15are constructed by hydrogen bonds. Complex16containes hexanuclear units [Pb3(COO)6]2, which linked through Fpht and Fba ligands to form2D network, and further extended into a final3D supramolecular via C-H…F hydrogen bonds. The fluorescence of complexes12-16comes from the π*-π transition of the ligands.