Budget Amount *help |
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1996: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1995: ¥1,400,000 (Direct Cost: ¥1,400,000)
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Research Abstract |
Recently, metal complexes with organic ligands have attracted much attention from the viewpoints of not only pure chemistry but also applied sciences such as material or biological science. In order to understand the detailed physicochemical nature of the complexes, knowledge concerning with behavior of electrons in the complexes may be very important. In this investigation, the electronic and the nature of electronic transitions of metal complexes formed between Cu (II), Ni (ii), Pd (II) etc.and organic ligands such as tropolene, catechol, N,N'-disalicylidene-o-phenylenediamine, 2,2'-dipyridine etc.have been elucidated, from the viewpoints of electronic absorption spectra, X-ray diffraction analyzes, and MO theories. For instance, (2,2'-dipyridine) (catecholato) copper (II) (abbreviated to Cu (cat) (bpy)) shows a d-d band around 650 nm, an intramolecular L-M (cat-Cu (II)) CT band at 425nm, localized transitions on the bpy skeleton at 312 and 261 nm, and localized transitions on the cat skeleton at 296 and 246.5 nm. Furthermore, it is found that the 322 nm band is due to an intramolecular ligand to ligand (cat to bpy) CT transition, i.e., an intramolecular LL CT transition. This means that the two pi electronic systems of cat and bpy skeletons, which can be considered to exist almost independently, interact significantly to each other. The complex, (catecholato) (1,10-phenanthroline) copper (II) (Cu (cat) (phen)), shows localized transitions on the hen skeleton at 331,308,275.0,267,233, and 227 nm, and on the cat at 295 and 210.0 nm. Although, in this case, an L-L CT transition from cat to hen has not been observed, it is interesting that the interaction of the two pi eletron systems localized on the cat and phen moieties is recognized through configuration interactions, the relevant band being observed at 209 nm.
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