Synthese, Structures, And Property Study Of New Coordination Compounds Based On Unsymmetric Ligands

The aim of this thesis is the synthesis of new coordination compounds on the basis of unsymmetric ligands (pyridine-3,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, 4,5-imidazoledicarboxylic acid, and 1,2,4-benzenetricarboxylic acid) and metal ions. The study on synthetic conditions and rules for these new compounds, topological analyses, and the exploration of relationships between structures and properties for these new compounds are also carried out.Twenty-nine new coordination compounds have been synthesized on the basis of hydrothermal technique and/or water solution synthesis methods and structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities, magnetic properties and fluorescent activity of these compounds have been studied.1. Twelve new compounds on the basis of pyridine-3,4-dicarboxylate (PDB) and coligands of different configurations have been hydrothermally synthesized and structurally characterized including six 3-D and three 2-D layered structures constructed by transition metals, and three 2-D frameworks constructed by lanthanide metals:[Zn(PDB)]_n(1)[Zn₂(PDB)₂(DMF)₃]n (2)[Cd₃(PDB)₂(OH)₂(H₂O)₂]_n (3)[Cd₂(PDB)₂(H₂O)]_n (4)[Zn₂(PDB)₂(4,4'-bpy)].H₂O (5)[Ni(PDB)(4,4'-bpy)].0.5H₂O (6)[Zn(PDB)(2,2'-bpy)]_n (7)[Cd(PDB)(2,2'-bpy)]_n (8)[Cd(PDB)(1,10-phen)]_n (9)[La₂(PDB)₂(NO₃)₂(H₂O)₃] (10)[Sm(PDB)(ox)_0.5(H₂O)₂]-H₂O (11)[Dy(PDB)(ox)_0.5(H₂O)₂]-H₂O (12)Compounds 1-4 have three-dimensional structures that are only constructed by PDB and d¹⁰ metals;compounds 5 and 6 are also show 3-D structures when linear ligand 4,4'-bpy is introduced;whereas compounds 7-9 exhibit 2-D frameworks when chelating ligands are introduced;the 2-D networks of compounds 10-12 are constructed by PDB and lanthanideions. Intriguingly, compound 4 is the first 3-D open framework constructed by molecular bilayers and compound 6 represents the first helical-pillared 3-D coordination network. In addition, the luminescent properties of those compounds containing ct metals and magnetic property of compound 6 are also investigated.2. Five 3-D coordination compounds have been hydrothermally synthesized by virtue of pyridine-2,5-dicarboxylate (pydc) and lanthanide ions:[Sm(pydc)(Hpydc)]n (13)[Eu(pydc)(Hpydc)]n (14)[Gd(pydc)(Hpydc)]n (15)[Sm(pydc)(bc)(H2O)]w (16)[Gd(pydc)(bc)(H2O)]w (17)Compounds 13-15 are isostructural and their 3-D frameworks are constructed by mononuclear lanthanide ions, exhibiting an unprecedented rutile-related (4.62)2(42.69.84) topology. Compound 16 and 17 are isomorphous, but the 3-D networks of them are constructed by binuclear lanthanide ions, displaying a distorted rutile (4.62)2(42.610.83) topology. The five compounds represent the first three-dimensional series of {Ln/pydc} system. Furthermore, the fluorescent spectrum of compound 14 was measured, which exhibits the characteristic transition of the Eu3+ ion.3. Five new compounds with different dimensionalities have been hydrothermally synthesized on the basis of 4,5-imidazoledicarboxylate (IDC) and transition/lanthanide metal ions:[Zn(H2IDC)2(H2O)2]n (18)[Cd(HIDC)(H2O)2]w (19)[Cd(HIDC)(phen)]? (20)[Sm(HIDC)(ox)o.5(H20)] (21)[Pr(HIDC)(ox)0.5(H2O)2]-H2O (22)[Sm2(IDC)2(H2O)3]-1.5H2O (23)[Eu2(IDC)2(H2O)3]-1.5H2O (24)[Gd2(IDC)2(H2O)3]-1.5H2O (25)Compound 18-20 show 3-D supramolecular networks constructed by H3IDC and d10 metals. Compounds 21 and 22 display 2-D structures constructed by H3IDC, ox and lanthanide ions. Compounds 23-25 exhibit novel 3-D open frameworks, in which the unusual five intersecting helical motif is the highest degree of entanglement ever found in rare earth chemistry.4. Four new compounds on the basis of 1,2,4-benzenetricarboxylate (BTC) and transition metal ions have been synthesized and structurally characterized:[Cu2(HBTC)2(H2O)2(^-H2O)]-2H2O (26)[Zn2(HBTC)2(H2O)3]n (27)[Ni3(BTC)2(4,4'-bpy)2(H2O)5]-1.5H2O (28)[Ni(4,4'-bpy)(H2O)4] [Ni(HBTC)2(4,4'-bpy)(H2O)2] -2H2O (29)Compound 26 exhibits arm-shaped two-dimensional layered structure. The three-dimensional architecture of 27 possesses rectangular 1-D channels. Compound 28 exhibits a unique helix-pillared 3-D architecture. Compound 29 contains crystallographically independent anionic and cationic polymeric chains. The fluorescent study on the compounds based on d10 metals and the magnetic properties of compounds 28 and 29 are also discussed.