The Structures And Catalytic Properties Of Coordination Complexes Built From Triangle N-Neterocycle/Flexible Carboxylate Ligand

Metal organic coordination compounds as a new composite materials combining inorganic and organic groups,have a wide range of applications in many areas,such as gas adsorption and separation,biological drug transport,electronic sensing,light capturer,magnetic materials,etc.In the field of catalytic especially heterogeneous catalysts,they also exhibit excellent performance.Metal organic coordination compounds have the adaptable structures and functions,specific surface area,the substrate selectivity,easily recycled and other superior characteristics.In process of the catalytic progress,its porous structure firstly capture the substrate,and then metal or ligand involve in catalysis as catalytic sites.Its specific structure with large-pore lead to special size and stereo lselectivity.Secondly,the applications of the crystalline porous complex material with multiple active sites in synergistic organic catalysis,tandem reactions proceed by one-pot synthesis method.So to develop more metal organic complexes as catalyst is a meaningful issue.In this study,two ligands a triazole nitrogen ligand N,N,N-tris(3-pyridyl)-1,3,5-benzenedicarboxamide(3-TPB)and a biscarbazole tetracarboxylic acid Ligand 9,9'-(propane-1,3-diyl)-bis(9H-carbazole-3,6-dicarboxylic acid)(H4pbcd)were used to.assemble eight complexes by hydrothermal method.The catalytic performance of the complexes were researched.The five complexes were synthesized by self-assembly of triazine ligands(3-TPB)and copper(I)salts,[CuI(3-TPB)]n(1),[(CuI)2(3-TPB)]n(2),[CuBr(3-TPB)]n(3),[CuBr(3-TPB)]n(4),{[Cu(3-TPB)]·Cl}n(5).They had different coordination modes and different crystal structures.The structure of Complexes 1,2 is one-dimensional strands.Complexes 3 and 5 are two-dimensional structures,while complex 4 is a three-dimensional structure.Interestingly,the chloride ions in the complex 5 are free.Reference to the catalytic ability of copper salts,the catalytic performance of the complexes 1,3,5 for C-H arylation is studied experimentally.The relatively ideal catalytic yield was got by screening the conditions.The differences in the catalytic performance of 1,3,5 complexes for C-H arylation were discussed.Then complexes 1,3,5 were further used to catalyze Alkyne-Azide "Click" reactions in the experiment,as a result the experiment got the ideal catalytic yield,and realized heterogeneous catalysis with catalyst circularly used.On the others side,in the synthesis of three complexes with dicarbazole tetracarboxylic acid ligands,{[Co4(pbcd)2(H2O)2]·(C2H5OH)·3(H2O)}n(6),{[Zn2(pbcd)(H2O)]·(H2O)·(C2H5OH)}n(7),{[Co2(pbcd)(bpe)]·2(H2O)}n(8).Complex 6 has two different quadruple Co clusters to form a three-dimensional structure.On the basis of complex 6,1,2-bis(4-pyridyl)ethane was added to obtain complex 8 with a three-dimensional structure wich is tremendously different from complex 6.Complex 7 possess a two-dimensional stepped structure.The acylatedNazarov cyclization reaction on the benzene ring was catalyzed by complexes 6,7,8,and good yield was obtained.Meanwhile,Complexes 6,7,8 could be recycled several times.