Conjugated Organometallic Systems and Development to Physical Properties

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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.