| This dissertation use the novel type polyaza-complexes as research objects,focusing on the study of the syntheses, characterizations, properties andtheory analyses of some novel polyaza-complexes: the macrocyclicpolyaza-complexes and branched hexamine complexes derived from N, N,N', N'-tetrakis(3'-aminopropyl)-alkyldiamine or N, N, N',N'-tetrakis(2'-aminoethyl)- alkyldiamine. The objective is to obtain thecoordination polymer with supermolecular self-assembly. The thirteen newcomplexes (1—13), ([Cu2L21](ClO4)2·MeOH, [Cu2L2](ClO4)2,[Mn2L2(H2O)2](ClO4)2, [Ni2L2(H2O)2](ClO4)2, [Cu2L3](ClO4)2, [Mn2L4(OAc)(H2O)2]ClO4, [Zn2L3(OAc)(H2O)](ClO4), [Cu2L4](ClO4)2, [Mn2L4(OAc)(H2O)]ClO4, [Ni2L4(OAc)(H2O)]ClO4, [Zn2L4(OAc)(H2O)]ClO4,[Cu2L5(μ2-Cl)2](ClO4)2 and [Cu4L6(μ2-Br)2(μ3-CO3)]Br(ClO4)3·2.5H2O, wereobtained and characterized by the MS, IR and NMR. The crystal structure ofsix complexes were determined by X-ray diffractions techniques. Theprotonation constants of the branched hexamine [H6L5]Cl6 were measured andcalculated by pH titration and relative calculation programs. Through theexperiment of cyclic voltammograms and variable-temperature magneticsusceptibility data of the complexes, the electro-chemistry characterizationand magnetism interactions between metal ions were studied.The work is composed of:1. Through four step reactions, such as acylation, hydroxylation, substitution,hydroxylation, two new hexamine salt compounds, named N, N, N', N'-tetrakis(2-aminoethyl)-1, 4-diaminobutane hexahydro chloride and N, N, N', N'-tetrakis(2-aminoethyl)-1, 4-diaminobutane hexahydrobromide have beenobtained with p-toluenesulfonyl chloride, ethanolamine, 1, 4-diaminobutaneas start materials. Protonation constants of the polyamine have been measuredand calculated through pH titration and relative calculation programs. A novelcopper (Ⅱ) complex (12) of hexamine has also been synthesized, the uniquesuper molecule self-assembly in the complex was first reported, and its crystalstructure was determined by X-ray diffractions techniques. The complexassumes one-dimensional chain structures linked byμ2-chloro groups whichwere found in solid state and water solution. The electrochemistry studiesshows that the complex behaves two pairs of redox peaks in the range ofpotential 0—-1.2V., in which all of them are irreversible. The study ofsusceptibility shows that the complex displays antiferromagnetic exchangeinteractions between the two copper (Ⅱ) in the complex.2. Through additional reaction and catalyzed additional reaction, a novelpolyamine named N, N, N', N'-tetrakis(3'-aminopropyl)-propane-1, 3-diamine,was first synthesized from acrylonitrile and propane-1, 3-diamine. A novelhexamine copper(Ⅱ) complex (13) has been synthesized and the structure wasmeasured by X-ray diffractions techniques. The complex assumes marlinestructure similar with DNA linked byμ2-bromine groups andμ<sub>3-carbonateions, and the complex takes same structures in the liquid solution as in thesolid state. The electrochemistry study shows that the complex behave twopair of redox peaks in the range of potential 0—-1.2 V, in which all of themare irreversible. The study of susceptibility shows that the complex displaysantiferromagnetic exchange interactions between the four copper (Ⅱ) in thecomplex.3. Ten symmetric macrocyclic complexes with different cavity have beensynthesized by stepwise template method with 2, 6-diformyl-4-florophenol and diamine as start materials. Their structures were characterized by ES-MSand IR. The X-ray diffraction results of the complexes 2, 5 and 8 reveal thatthe coordination structures of Cu2+ in the complexes are an elongatedoctahedron structure. Except the complex 2 which is in the form of "Z" shapeand does not connect by perchlorate ion, the complexes 5 and 8 are chaincoordination polymers which exhibit ship-shap structure and connect witheach other by the supermolecule self-assembly formed through twoμ2-ClO4.The results of HPLC show that they are in the polymeric state in watersolution. The electrochemistry studies show the complex 2 behave twodeoxide peaks and complex 5 and 8 behave two pair of redox peaks in whichone of them is reversible and another is pseudo-reversible in the range ofpotential 0—-1.2 V. The study of susceptibility shows that the complexesdisplay strong antiferromagnetic exchange interactions between the twocopper (Ⅱ) in the complex.4. A new acyclic complex was synthesized by stepwise template method with5-fluoro-2-hydroxy-3-hydroxymethyl-benzaldehyde and N1-(2-Amino-ethyl)-ethane-1, 2-diamine as starting materials in the presence of copper (Ⅱ),and this complex was characterized by ES-MS and X-ray diffractionstechniques. The result reveals that the complex is a dimmer and the dimmershould break down in the solution. The electrochemistry study shows thecomplex behave one pair of redox peak in which it is a pseudo-reversible inthe range of potential 0—-1.2 V.
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