The Synthesis, Crystal Structure, Properties And Theoretical Studies On The Compounds Of Terpyridyl And Crown Ether

In this thesis,the following research contents are reported:1.A series of 4"-substituted 4’-phenyl-2,2’:6’,2"-terpyridine compounds L1-L8 were synthesized,in which substituted groups are hydrogen,methoxyl,methylsulfonyl,cyano,methyl,phenyl,iodo,or p-methyl-phenyl.They are characterized by IR,elemental analysis,X-ray determination and their photoluminescent properties were also studied.It was found that the hydrogen bonds of the N atoms of the middle and terminal pyridyl rings have the effect on the luminescent behavior in low energy region(λ>500 nm)in this terpyridine system.Inspired by this phenomenon,two equations were reported to predict their emission wavelength of these compounds basing on L1,to calculate emission wavelength of photoluminescence with the lengths of hydrogen bonds and to propose the mechanism for the process.The relationship between photoluminescence and the substituted groups has been systematically investigated by comparison of the spectroscopic measurements and density functional theory calculations(two methods:a.crystal structures;b.optimization of designed structures).2.Basing on the synthesis and characterization of 4"-methylsulfonyl-4’-phenyl-2,2’:6’,2"-terpyridine(L3)in the PART I,complexes[ZnCl2L3](1)、[Zn(L3)2]·(p-S03PhCH3)2(5)and[Ag(MeCN)L3]SbF6(6)were synthesized,and the crystal structures were determined by X-ray diffraction.The results indicate that L3 is triclinic system while 1,5 and 6 are monoclinic system.The geometry of metal ion in 1 is square trigonal biyramid,and that in 5 is octahydron while in 6 is square planar.In these compounds,the hydrogen bond and strong π-π stacking interaction act as the key-role to form the 3D net-system.For the purpose to gain insight into the luminescent bahavior of zinc complexes of L3,complexes[ZnBr2L3](2)、[ZnI2L3](3)and[Zn(N03)2L3](4)were synthesized and perform their fluorescence in solid-state.The results indicate that the coordination environment of centra metal cations(coordinate anions or coordination number)in these zinc complexes has the impressive effects on their luminescent behavior.3.Reactions between the N604 macrocyclic 1,4,23,26,29,48-hexaaza-6,9:16,19:31,34:41,44-tetrabenzo-12,15,37,40-tetraoxa-cyclodotetracontane(L9)and several copper salts led to the formation of the dinuclear complexes[Cu2(OSO2CF3)2(DMF)2L](SO3CF3)2(7),[Cu2(p-OSO2C6H4Me)2L(DMF)2](SO3C6H4Me)2(8),[Cu2(ONO2)2L(DMF)2](NO3)2(9),[Cu2(OClO3)2(DMF)2L](ClO4)2(10),[Cu2(OOCPh)2L(H2O)2](O2CPh)2(11)and[Cu2(OOCMe)4L](12)which were characterized by IR,elemental analyses,EPR and electrochemical techniques(cyclic voltammetry and controlled potential electrolysis),moreover,complexes 7,9 and 10 were characterized by single crystal X-ray diffraction.The molecular structures of 7-12 reveal a considerable conformational flexibility of ligand L9,which allows the readjustment of the ligand for the formation of the dinuclear metal complexes in endo conformation macrocyclic species.In every case L9 ligand coordinates to each copper cation by three nitrogen atoms,the remaining coordination positions of the metals being occupied by neutral or anionic ligands in a square,pyramidal,environment.The.compounds,in combination with 2,2,6,6-tetramethyl-piperidinyloxyl(TEMPO)radical and in alkaline aqueous solution,act as efficient catalysts in the aerobic oxidation of different alcohols to the corresponding aldehydes(yields up to 99%and TON up 232)after 20 h at 70℃.In addition,the microwave-assisted solvent-free peroxidative oxidation(by tert-butylhydroperoxide,TBHP)of 1-phenylethanol led to acetophenone yields up to 99%and rTOF of 1.1×103 after 0.5 h,without any additive.