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Bridged Polynuclear Complexes Synthesis, Characterization And Performance Study

Posted on:2003-12-08Degree:MasterType:Thesis
Country:ChinaCandidate:H L WangFull Text:PDF
GTID:2191360062490079Subject:Inorganic Chemistry
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The design, synthesis and characterization of a series of polynucleartransition-metal complexes using complexes as ligand , as a basis of this paper, focus on systematically dealing with the magnetic properties, biological activities and electrochemical behavior, according to the main routes of designing magnetic molecules. In this paper, element analyses, IR,UV, ESR spectra have been used to characterize these complexes. According to the coordination field theory and molecular orbital theory and with the help of computer calculation, the structures, the quantity and quality spin exchange interaction of these complexes have been proposed. This paper can be divided into four parts:1. Eleven new N,N'-bis(3-aminO'2,2-dimethylpropyl)oxarnido-bridgedCu3"Lnm-type (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Yb) heterotetranuclear complexes have been synthesized . The reaction may beexpressed as the following equation: 3Cu(Me2oxpn) + Ln(NO3)3-6H2O - [Cu3(Me2Oxpn)3Ln(NO3)](NO3)2(Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Yb) Results have confirmed that these complexes have oxamido-bridged structure consisting of a lanthanide(III) ion and three copper(II) ions. The temperature dependence of magnetic susceptibilities of the heterotetranuclear [Cu3(Me2oxpn)3Gd(NO3)](NO3)2 complex was measured and analyzed over the range 4.2~300 K, demonstrating that there is a very weakly ferromagnetic spin-exchange interaction between lanthanide(in) ion and copper(II) ions with the exchange integral J = +3.88 cm"1 and g = 2.01.2. Two new N,N'-bis(3-amino-2,2-dimethylpropyl)oxamido-bridged [Cu(Me2oxpn)Mn(tmen)2](ClO4)2 and [Cu(Me2oxpn)Zn(bpy)2](ClO4)2 heterobinuclear complexes have been synthesized and characterized, where tmen and bpy stand for N,N,N'N'-tetramethylenediamine and2,2'-bipyridine, respectively. The reaction can be expressed as thefollowing equation:Cu(Me20xpn)+Mn(ClO4)2+tmen - [Cu(Me2Oxpn)Mn(tmen)2](ClO4)2 Cu(Me20xpn)+Zn(ClO4)2+bpy -籟Cu(Me2Oxpn)Zn(bpy)2](ClO4)2 It is proposed that these complexes have oxamido-bridged structuresconsisting of a copper(II) ion and a M(II) ion(M = Mn, Zn). The magnetic moments of these complexes have been measured and studied. In order to further prove the relationships between structure and function, the effects of these binuclear complexes on the wheat growth were also studied. Research found that these binuclear complexes were benefit to the wheat growth.3. Two new u-oxalato-bridged (VO)3lvCu"-type heterotetranuclear complexes have been synthesized and characterized by element analyses and IR. The reaction can be expressed just as the following equation:3[VO(C204)L]+ Cu(C104)2-6H20- {[YO(C2O4)L]3Cu}(ClO4)2(L = bpy, phen)It is proposed that these complexes have oxalato-bridged structures consisting of three oxovanadium(IV) ions and a copper (II) ion. The electrochemical behavior of heterotetranuclear complex{[VO(C2O4)(bpy)]3Cu}(ClO4)2 on a platinum electrode was investigated using cyclic voltammetry.4. The thermal decomposition of [VO(C2O4)(bpy)]-2H2O and [VO(C2O4)(phen)]-H2O complex under dynamic air atmosphere was studied by TG and DTG techniques. The nonisothermal kinetics data were analyzed by means of the Achar method and the Coats-Redfen method. Through comparison of the kinetic parameters, the most probable kinetic model function was proposed. The mathematical expressions of E and InA were derived from the kinetic compensation effects.
Keywords/Search Tags:oxamido-bridged, oxlato-bridged, synthesis, characterization, magnetism, biological activity, electrochemistry thermal decomposition, non-isothermal kinetics
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