Styntheses,Structures And Property Studies Of Coordination Polymers With Carboxyl And N-containing Heterocyclic Ligands

In recent years, containing carboxylic acid and heterocyclic ligand complex developmentrapidly has become a research focus of the field of materials chemistry. In accordance withthe principle of crystal engineering, the method of synthesis of crystalline materials in general,select a specific ligand configuration of the central metal ion and functional organic ligands.In this article, we have selected a transition metal or rare earth metals, and carboxylic acidsand nitrogen-containing ligands,, the synthesis of nine new functional coordination polymersunder hydrothermal and solvothermal synthesis method. Crystal structure analysis, elementalanalysis and IR, TGA, and some compounds of the fluorescence properties are characterized.1. We have prepared three new NiIIand CoIIcomplexes by changing the N-donorauxiliary co-ligands which include rigid ligands （4,4’-bpy） and flexible ligands （bbi） under thehydrothermal condition.{NiL¹（4,4’-bpy）}n（1）{NiL¹（bbi）}n（2）{[Co（4,4′-bpy）（H₂O）₄]·(H_3/2OABDC)·5H₂O}n（3）Complexes1is1D tubular structure which is linked into the2D supramolecular by thenon-covalent interactions （C–H···O）. Complex2shows2D sheet structure. For complex3,1D linear chain and2D hydrogen-bonded sheet for2) can be found within their crystalstructures, and most intriguingly, they coexist in such a way that1D covalently bonded chainsof composition [Co（4,4′-bpy）（H2O）4] thread into the hydrogen-bonded3D formed byuncoordinated carboxylate anions and lattice water molecules.2. Two complexes,[Ln2H3/2OABDC（H2O）4]n[Ln=Sm （4）, Eu （5）], synthesized by thehydrothermal reaction of a unique scorpion-shaped carboxylate ligand （5-oxyacetateisophthalic acid=H3OABDC） with different lanthanide.[Sm₂H_3/2OABDC（H₂O）₄]n（4）[Eu₂H_3/2OABDC（H₂O）₄]n（5）Compounds4–5are isostructural: the metal ions are bridged through rigid carboxylateand flexible oxygen atoms to form1D double zigzag chains, and adjacent chains are furtherextended to a3D supramolecular structure via hydrogen bonds. Compounds4and5presentcharacteristic emission of Eu（III） and Sm（III） in the visible region, respectively.3. A series of lanthanide complexes,[LnL¹L²_1/2（H₂O）₂]n[Ln=La（6）, Sm（7）, Gd（8）,Eu（9）, H2L¹=2,4-bis（4-methylbenzoyl）isophthalic acid and H₂L²=2,5-bis（4-methylbenzoyl）terephthalic acid] have been prepared under hydrothermalconditions. {LaL¹L²_1/2（H₂O）₂}n（6）{SmL¹L²_1/2（H₂O）₂}n（7）{GdL¹L²_1/2（H₂O）₂}n（8）{EuL¹L²_1/2（H₂O）₂}n（9）Complexes6-9are isostructural and comprise paddlewheel dinuclear lanthanidesecondary building units linked by four carboxylic groups. L1ligands link the dinuclearlanthanide building blocks to form one-dimensional double-stranded looplike chains. Thechains are further connected to two-dimensional layers by L2.