| Budget Amount *help |
¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 1998: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1997: ¥1,800,000 (Direct Cost: ¥1,800,000)
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| Research Abstract |
1)Preparation of Ligands Eight pyridylporphines 5-R_1-1O-R_2-15-R_2-20-R_4-porphine H_2P^1-H_2P^1 were prepared. a)Through change in adding order of reagents, H_2P^1 (R_1=4-pyridyl(4-py), R_2=R_3=R_4-phenyl (phi))) and H_2P^2(R_1=R_3=4-py, R_2=R_4=phi ) were obtained in several time yields as compared with known method. Correspoding 3-py derivatives H_2P^3 and H_2P^4 were obtainedin similar manner.
b) Reaction of TsOCH_3 with tetrapyridylporphine gave H_2P^5 (R_1=R_3=4-py, R_2=R_4=N-methyl-4-pyrldinium(4-py-CH_3^+) together with cis-derivative H_2P^5.1.H_2P^5 and TsOCH_3 afforded H_2P^7(R_1=4-py, R_2=R_4= phi , R_3=4-py-CH_3^+). H_2P^8 (R_1=4-py, R_2=R_4= phi R_3=H) was synthesized from pyrrole and thiophosgene.
2)Synthesis of Comprexes ZnP^1, ZnP^3, ZnP^2RUpy_2^+, ZnP^5RUpy_2^<3=> and [ZnP^7]^+ were synthesized from corresponding H_2P and Zn(CH_3COO)_2 and / or [Ru_3(_<1_3-O )(>1-CH_3COO)_6py_2 (CH_3OH)]PF_6 (abbreviated by RUpy_2(CH_3OH)^+).
3)Cyclic Oligomer Insoluble component of ZnP^3 in CH_2CI_2 was oxidized with AgPF_6 to afford blue-violet solid with composition [(ZnP^3)_<12>]PF_6)_6・ 2C_6H_<14>. It gives spectroscopic and electrochernical data consistent with [(ZnP^3)_6(ZnP^3・^+)_6]^<5+>.
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