| Summary: | 碩士 === 淡江大學 === 化學學系 === 84 === A series of copper(I) and copper(II) complexes has
beenprepareed,containing -diimine ligands, PPA and PTA. Thereare
ten complexes listed below[Cu4(PPA)4](ClO4)4,,[Cu2(DMP)2(PPA)](
ClO4)2,[Cu4(PPA)4][Cu3Br6][CuBr2], [Cu4I4(PPA)2],[Cu(II)(PPA)2
I]I, [Cu(II)(PPA)2I]ClO4,[Cu4(PPA)4][Cu4Cl8], [Cu4I4(PTA)2],
[Cu4Br4(PTA)2] and[Cu4Cl4(PTA)2] ,the front six complexes whose
molecularstructures are confirmed by X-ray crystal diffraction.
Tosum up, these copper(I) complexes exhibit distortedtetrahedral
coordinate structure.The N-Cu-N angles isabout 80 and 120. The
Cu-N distance is nearly1.989~2.115. We also discuss their
elemetal analysis, IR, MS, andNMR in detail. To study the
electronic state by researchtheir electronic absortion and
emission spectrum. Byelectronic absortion spectrum, we can
observe transitionof ligand between 255~300nm. About emission
spectrum, wecan also observe emission from and d states at
385nm and520nm. The redox properties of [Cu4(PPA)4]4+ complex
areinvestigated by cyclic voltammetry. The [Cu4(PPA)4]4+complex
undergoes four step one-electrole reductions onthe PPA ligands
in the -0.80V~-1.23V. But the existenceof counterion Cl-,Br-,I-
in [Cu4(PPA)4]4+ complexes willresult dissociation of the
complexes. In addition, the[Cu4(PPA)4]4+complex undergoes three
step one-electronreduction on the PPA ligands in the -1.64V~-2.4
V. Howeverthe dissociation process will take place with
reductionon the copper ion. In the oxidation behavior, all
theoxidation reaction occur on the copper ion, and shows
theirreversible or quasi-reverible.
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