Synthesis And Properties Studies Of 3d Metal Coordination Polymers Constructed With Pyridine-carboxylate Ligands

In recent years,Metal-organic frameworks(MOFs)functional coordination polymers is a challenging and hot research topic in inorganic chemistry,pillared-layer type MOFs which is one of the representative of microporous metal complexes,and have been extremely concerned by the chemistry and materials science scientists.MOFs study was driven by Japanese professor S.Kitagawa group and other chemisty scientist,the pillared-layer type compounds have made substantial progress,which exhibits unique properties in the selective catalytic,selective separation,gas energy,molecular recognition,light/electric/magnetic functions,drug controlled delivery,biomedical and a lot of direction of other areas.Reasonable design polydentate carboxylic acid ligands for the expand layer ligand,assisted with appropriate linear bridging ligands is an effective means to build pillared-layer type MOFs,In the earlier work of our group:on the basis of successfully obtain the type of pillared-layer MOFs,which mainly choose flexible aliphatic polycarboxylic acid 1,2,3-propionic acid,and fumaric acid ligands as the layer,4-(4'-pyridyl)biphenyl-4-carboxylic acid root,4-(4'-pyridyl)benzoate,isonicotinic group as bridging pillar ligand,successfully constructed two new pillared-layer MOFs,which using more longer pillar ligand(HPybbz=4'-Pyridin-4-yl--biphenyl-4-Carboxylicc Acid).With the longer of the pillar ligand,its solublity decrease and result in orientation to construct more and more difficult.While our group have rich experience on directional pillared-layer MOFs,then successfully overcome this difficulties.The structure of the compounds,their synthesis conditions,thermochemical stability,adsorption behavior and magnetic properties were characterized and research.Meanwhile,using a few new and important hydrothermal synthesis strategies.including in-situ metal/ligand reaction.ligand-structure directing.templating.as well as reaction-condition tuning(temperature,pH,solvents,etc.),have been synthesized of novel structurals and interesting coordination polymers.This thesis has three chapters.The first chapter is the preface,describe the background and development of the MOFs research,systems analysis about research progress of pillared-layer type MOFs,discusses the significance of the topic and the progress made in this thesis.In the second chapter,We use the 1,2,3-propane tricarboxylic acid as the layer ligand and pyridyl monocarboxylic ligands as a to pillar obtained one iron base pillared-layer microporous metal-organic frameworks[Fe5(OH)2(tca)2(pybz)2(PrOH)2]·4H2O(4).When using the longer pillar ligand,such as 4-(4'-pyridyl)biphenyl benzoate(pybbz),and was successfully to get another three similar cases of cobalt-based pillared-layer structures[Co5(OH)2(tca)2(pybbz)2(PrOH)2]·2H2O(1);[Co5(OH)2(tca)2(pybbz)2(EtOH)2]·2H2O(2)and[Co5(OH)2(tca)2(pybbz)2(i-PrOH)2]·2H2O(3).Compare with the former compounds[Co5(OH)2(tca)2(ina)2(H2O)2]·4H2O(1a)and[Co5(OH)2(tca)2(pybz)2(PrOH)2]·2H2O(1b),We controlled the channel size by simple modification of the pillar's length from isonicotinic acid(4.97 (?))to 4-pyridin-4-yl-benzoic acid(9.18 (?)),and to 13.4 (?),and the void volume raise from 10.4%to 32.3%,and to 34.7%;channel size raise from5.2 × 4.5 (?)2,8.6 × 4.5 A2 to 13.2 × 4.5 A2.This series of compound show a high temperature resistant characteristics of the thermal stability and strong acid and alkali resisitant.The study of gas adsorption presents obvious gate-open behavior at the CO2 uptake,which show a flexible framework.Base on this work and 2006 Dalton our group's work,another pillared-layer type compound[Co2(pybbz)(ma)]·PrOH·H2O(5)successfully constructed by the fumaric acid group(ma)as the layer ligand,and 4-(4'-pyridyl)diphenic acid root(pybbz)for flexible ligand under hydrothermally conditions.Compare with our group's another two compounds[Co2(ina)(ma)]·2H2O(5a)and[Co2(pybz)(ma)]·4H2O(5b),they suing the shorter pillar ligand,isonicotinic acid(ina)and 4-(4 'pyridyl)benzoic acid(pybz)as the rigid bridging pillar.The three structures contains the similar layer,and the void volume raise from 25.8%to 32.3%,and to 36.3%due to pillar's length.using the Bruker Smart CCD diffractometer probe on room temperature(in situ)determination of the crystal structure of the series compounds.And the TG/DTG curve of them in N2 show that these complexes have striking thermal stability.We also have studied inclusion and magnetic properties in the later work.In the third chapter,mainly introduces the solvent thermal conditions,using the linear benzene carboxylic ligands(pybbz)and thiamethoxam thiazole linear benzene carboxylic ligands(H2L)orientation to construct two cases with chain pillar type diamond window microporous coordination polymer Fe(pybbz)2·DMF(6)and Mn2(H2L)·DMF(7).The former compound has a 1D channel in a direction with a Vvoid was 48.8%,thermogravimetric analysis showed that its framework can stable up to 380?.We studied the adsorption behavior of the gas.The second compound also has a one dimension channels in c direction with 25.7%void space.thermogravimetric analysis showed that its framework can stable up to 420?.The 195K CO2 sorption isotherm of 7 follows the typical type I characteristic of microporous materials with a BET surface area of 420 m2/g and Langmuir surface area of 527 m2 g-1.