Budget Amount *help |
¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1991: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1990: ¥700,000 (Direct Cost: ¥700,000)
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Research Abstract |
The main purpose of the present research project is the detailed measurements of vibrational fine structure of the ligand-field absorption bands of Co(III) and Cr(III) complexes at low temperatures. Special interest is focused on the absorption bands of the complexes which have relatively simple structure involving NH_3, CN^-, en:ethylendiamine, tn:1,3-propanediamine as ligands. Strategy of the present project is to apply the mixed-crystal technique in the low temperature absorption measurements. The vibrational fine structures should be studied on, firstly, the absorption transitions between orbitally non-degenerate electronic states. The low symmetry monocyano- and trans-biscyano-ammine complexes of Co(III) and Cr(III) complexes are the most suitable examples for this kind of research. Therefore, in the present study the preparations of the new corresponding Rh(III) complexes, such as trans-[Rh(CN)_2(NH_3)_4]^+, trans-[Rh(CN)<@22(en)<@22@>D2]<@D1+@>D1, and trans-[Rh(CN)<@D22@>D2(tn)<
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@D12@>D1]+, which are transparent in visile region and could give the suitable host lattices for the Co(III) and Cr(III) complexes, are involved as the most important stage. These series of the complexes could be successfully synthesized via trans-[RHCl<@D22@>D2(N-N)<@D22@>D2]<@D1+@>D1, trans-[Rh(SO<@D23@>D2)<@D22@>D2(N-N)<@D22@>D2]<@D1-@>D1, trans-[Rh(CN)(SO<@D23@>D2)<@D22@>D2(N-N)<@D22@>D2], trans-[Rh(CN)Cl(N-N)<@D22@>D2]+ (N-N)<@D22@>D2 =(NH<@D23@>D2)<@D24@>D2,(en)<@D22@>D2,(tn)<@D22@>D2, respectively. The mixed-crystals are preparing. For example, a good samples of trans-[Rh(:Co)(CN)(NH<@D23@>D2]<@D24@>D2]Cl.H<@D22@>D2O was already obtained. As another channel of the present project, the single-crystal polarized absorption spectra of [Cr(CN)(NH<@D23@>D2)<@D25@>D2]Cl・(ClO<@D24@>D2) are studied at low temperatures using the specially designed sample holders, and identified low symmetry splitting of the ligand-field electronic excited states including spin-doublets as well as spin-quartets. Less
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