Synthesis,Structures And Properties Of Supramolecular Compounds From Long Flexible Dicarboxylic Acids With Styrene Groups,Dipyridyl Ligands And Metal Ions

Functional metal-organic supramplecular polymers have been the focus of great interest due to not only their novel architectures but also potential applications as advanced materials in luminescence,gas storage,catalysis,separations and so on.The long flexible dicarboxylic or polycarboxylic acids containing styrene groups are good candidates for the self-assembly of functional supramplecular polymers with helical,interpenetrating or intertwisting architectures,because of their diverse configurations and coordination models,as well as hydrogen bonding and ?-? interaction of aromatic rings.However,above carboxylic acids have not been explored in depth in supramolecular chemistry.In this thesis,the long flexible(2E,2'E)-3,3'-((propane-1,3-diylbis(oxy))bis(2,1-phenylene))diacrylic acid(H2ppa)was used as O-ligand.The different dipyridyl ligands,1,2-di(4-pyridyl)ethylene(bpe),1,4-bis[2-(4-pyridyl)ethenyl]benzene(bpeb),4,4'-bis[2-(4-pyridyl)ethenyl]biphenyl(bpep),2,2-bipyridine(2,2'-bpy),4,4-bipy ridine(4,4'-bpy),served as the N-ligands.Under the solvothermal conditions,from the O-liand,N-ligands,and metal salts,eight supramolecular compounds have been synthesized,namely,{[Zn4(bpe)3(ppa)4](H2O)6}n(1),[Cd(ppa)(bpe)]n(2),[Zn2(ppa)2(bpeb)]n(3),[Co2(ppa)2(bpeb)](4),[Zn2(ppa)2(bpep)]n(5),[Zn(Hppa)2(2,2'-bpy)](H2O)(6),[Zn2(ppa)2(4,4'-bpy)]n(7),and [Co2(ppa)2(4,4'-bpy)]n(8).Wherein the compounds(3)and(4),(7)and(8)are isomeric compounds,respectively.In the experiment,key control factors on the supramolecular self-assembly,such as pH value,solvent,temperature and reactant ratio had been studied.The new compounds were characterized by X-ray single crystal diffraction,infrared(IR)spectoscopy and thremo-gravimetric(TG)and fluorescence test.X-ray single crystal diffraction revealed that compounds 1-5 exist two differentkinds of one-dimensional(1D)ladders separately possessing M(left-handed)or P(right-handed)helical information.Compounds 1,3 and 5 are two-dimensional(2D)coordination polymers,and form three-dimensional(3D)supramolecular structures by interlocking,respectively.In the interlocking regions of compounds 1 and 3,two different left-handed helix and right-handed helical structures are alternately arranged.The flexible ligand ppa2-presents different conformation and coordination models.Futher more,in the compound 5,there has the nano-sized rings of 18.98 ? × 16.27 ?dimension.Of compound 2,in the bilateral of 2D coordination structure from ppa2-ligands and metal ions,there exist M(left-handed)or P(right-handed)helical structures from corresponding helicates.The N-likers bridge the 2D layers to generate a 3D coordination network.Compound 6 is a zero-dimensional structure similar to the English letter "W",and compound 7 is also a pillar three-dimensional coordination polymer with a helical structures.The wavelengths of above compounds range from blue to yellow luminescence,and the relations between photosensitive properties with corresponding electronic structures are investigated.All above structures and properties reveal that the long flexible carboxylic acids facilitate the self-assembly of supramolecular compounds with helical,interlocking or other structural characters.The conjugate syrene groups play a very important role in the lang-wave luminescence of titled compounds.