Syntheses And Structures Of Coordination Compounds With N-containing Heterocyclic, Carboxyl And Schiff Base Ligands

Carboxylic acid and its derivates are of very important organic compounds, which are wildly used in industry, agriculture, national defense and other fields; Schiff bases and their metal complexes are very important compounds because their core group C=N has chemical and biological significance; Hitherto, research work is being done by researchers in the world, who have synthesized and estimated a plenty of Schiff bases and their metal complexes, studied and exploited many uses, such as catalyst, antibacterial medicines, material etc; Due to their potential applications in the fields of light, electricity, magnetism, catalysis, gas adsorption, etc., together with their controllable structural frameworks, complexes are considered to be the most promising functional materials and exhibit attractive prospects, and they have become one of the hot research realms in inorganic chemistry and materials. Herein, based on the current research in the field of coordination chemistry, we designed and synthesized 20 complexes and the network topology types of some complexes were studied.1 Elevent complexes (1-11) contained Cu(Ⅱ),Ni(Ⅱ),Mn(Ⅱ),Nd(Ⅲ) and Cd(Ⅱ) ions are designed and synthesized in order to study the catalysis of coordination complexes. Single crystal X-ray diffraction shows that coordination polymer {C14H6N2K2O8Zn·7.5H2O}n 1 displays infinitely extended two-dimensional reticulation structure but {[C28H12N4Na4O16Zn2·17H2O]}·5H2O 2 exhibits discrete binuclear structure though they have the same ligand pyridine-2,6-dicarboxylic acid but K(Ⅰ) as ion in 1 and Na(l) in 2. Using 2,4-dihydroxypyrimidine-4-carboxylic acid as ligand, complex [Cu(dpc)(phen)·H2O][Cu(dpc)(phen)]·7H2O 3,[Cu(dpc)(bpy)·H2O](ClO4) 4,[Mn(dpc)2(CH3OH)2]·CH3OH 5 and [Nd(dpc)2(phen)·3(H2O)]·4H2O 6 were obtained; Using 4,8-dihydroxyquinoline-2-carboxylic acid as ligand, complex {[Ni2(dqc)2(phen)2][Ni(phen)3]}·15H2O 7 was obtaind; Using benzene-1,3,5-tricarboxylic acid as ligand, coordination polymer{[Cd3(trim)2·9H2O]·H2O}n8 was obtained; Using N-containing ligands. coordination polymer [Cu(btx)2Cl2]n9 and two heteropoly acid anion containing complexes [(bix)4(Mo8O26)2] and [Cu2(dpip)4(H20)2(SiMo12O40)] 11 were obtained. (H2dpc= 2.4-dihydroxypyrimidine-4-carboxylic; H2dqc= 4,8-dihydroxyquinoline-2-carboxylic acid:phen = phenanthroline; bpy= 2,2'-bipyridyl; btx= 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene; H3trim= trimesic acid; bix=1,4-bis(1H-imidiazole-1-ylmethyl)benzene; and dpip= 1,3-di(1H-benzimidazol-1-yl)propane).2 A comparison of homogeneous vs heterogeneous catalytic activity for the oxidative coupling of 2,6-di-tert-butylphenol(2,6-DBP) by the aforementioned complexes 3,4,7,9 and 11 is performed by using H2O2(30% mass) as anoxidant in aqueous medium at elevated temperature. The results indicate that the complexes as heterogeneous catalysts record the higher conversion. Moreover, the experiment results showed that the catalytic activities of these complexes containing Cu11 ion are higher than that compound containing Ni11 ion.3 By the condensation of equimolar amounts of salicylaldehyde with N-substituted-1,2 or 1,3-diamine in methanol solution the Schiff base HL1～L8 were synthesized and separated. All these mononuclear crystals characterized by X-ray diffractometer showed that they have strong M-N bond and the existent of X- have no effect on the syngoney (X-= Cl-,Br-,orI-,).4. These Schiff base complexes have same metal ions, anions and different Schiff base ligands, or different metal ions, anions and similar structures. The influences of metal ions, anions, solvents, et al. on structures are researched and some rules are observed.