Grant-in-Aid for Specially Promoted Research
|Allocation Type||Single-year Grants|
|Research Institution||Osaka University(1995-1996)|
Okazaki National Research Institutes(1994)
NAKAMURA Akira Osaka Univ., Graduate School of Science, Professor, 大学院・理学研究科, 教授 (80029404)
TAKEDA Sadamu Gunma Univ., Faculty of Engineering, Associate Professor, 工学部, 助教授 (00155011)
MORI Wasuke Kanagawa Univ., Faculty of Science, Professor, 理学部, 教授 (60029709)
OKAMURA Taka-aki Osaka Univ., Graduate School of Science, Assistant Professor, 大学院・理学研究科, 助手 (90252569)
NAKANO Masayoshi Osaka Univ., Graduate School of Science, Assistant Professor, 大学院・理学研究科, 助手 (80252568)
YAMAGUCHI Kizashi Osaka Univ., Graduate School of Science, Professor, 大学院・理学研究科, 教授 (80029537)
中山 祐正 大阪大学, 大学院・理学研究科, 助手 (20273576)
真島 和志 大阪大学, 基礎工学部, 助教授 (70159143)
|Project Period (FY)
1994 – 1996
Completed(Fiscal Year 1996)
|Budget Amount *help
¥262,000,000 (Direct Cost : ¥262,000,000)
Fiscal Year 1996 : ¥15,000,000 (Direct Cost : ¥15,000,000)
Fiscal Year 1995 : ¥125,000,000 (Direct Cost : ¥125,000,000)
Fiscal Year 1994 : ¥122,000,000 (Direct Cost : ¥122,000,000)
|Keywords||Conjugated Organometallic System / Metal-Metal Multiple Bond / Hydrogen Bond / Magnetic Property / Solid State NMR / MO calculation / Nonlinear Optical Property / dpi-ppi interaction / 水素結合 / 金属触媒反応制御 / シクロペンタジェニル / シクロペンタジエンル|
A systematic synthetic strategy to straight linear polynuclear M'-M-M-M' (M'= Pd, pt ; M =Cr, Mo) complexes was established by using a unique tridentate ligand. The Mo_2Pd_2 tetranuclear complex showed very large third order nonlinear optical activity of x^<(3)> =1.2*10^9 (esu) comparable to that of poly (diacetylene) s.
A series of transition metal (Zr, Ru) polyene complexes were synthesized. In particular, the triene and diene complexes of zirconium bearing two cyclopentadienyl (Cp) goups were found to have remarkable thermochromism in the solid state. This can be attributed to the rotational tunneling of the Cp rings as indicated by ^<13>C-CP/MAS NMR spectroscopy at cryogenic temperatures.
The bond natures for di-and tetra-nuclear complexes including Cr (II) and Mo (II) were investigated by using ab initio methods. The effective exchange integral J for these systems were calculated to elucidate all possible magnetic phases. The electronic states of d-d conjjgated systems were found to be calculated precisely by considering the non dynamical correlations, included by using UNO CAS CI and CAS SCF methods, while for reproducint the electronic states of d-p cpnjugated systems, the dynamical correlations were found to be indispensable.
A number of microporous copper (II) dicarboxylates, molybdenum (II) dicarboxylates, and ruthenium (II,III) dicarboxylates which include a large amount of gases such as N_2, O_2, and CH_4 were synthesized. The molybdenum compound showed weak electric conductivity indicating the existence of -Mo Mo-Mo Mo- linear chain.
Novel conjugated systems involving NH・・・S and NH・・・O hydrogen bonds and neighboring transition metal ions have been synthesized. Significant contributions of these metal ions have been found ; regulation of acidity of the ligand, stability of metal-ligand bond, redox potentials of the system, magnetic properties, and so on.