MOLECULAR DESIGN AND SYNTHESIS OF COMPOSITE BI-AND POLY-NUCLEAR COMPLEXES.

本研究利用[Pt (4-mpyt) _4] ^<2+>的金属结合能力，制备了复合双核配合物。后期过渡金属如Ni （II）和Co （II）可以加入该体系，收率适中。Pt （II）和Co （II）的配合物均为方形平面结构，而Ni （II）和Co （II）的配合物均为四方锥体结构。与Co或Ni的顶端连接有助于系统的稳定。两种配合物在氧化成d^7-d^7体系时均增加了金属间相互作用，在形式上该体系不存在明显的相互作用。特别是，[Pt^<III> (4-mpyt) _4Co^<II>X]具有很强的金属间相互作用，从而产生抗磁性。早期过渡金属可以以V=O或Cr=O的氧化物形式掺入。特别是，Cr （IV）在该体系中具有非常独特的配位球，这是单核体系中从未出现过的。此外，Cr （III）配合物[Pt (4-mpyt) _4Cr^<III>Cl]被5个在Cr （III）状态下从未出现过的方形锥体形式的连接原子所包围。x射线结构结果显示如下证据。(1)无论早或晚，第一过渡金属都能形成[Pt (4-mpyt) _4MX]分子。与软S原子相比，4个N原子与第一过渡金属的配位是由于硬金属的偏好。(3)当[Pt (4-mpyt) _4Cr=O]或[Pt (4-mpyt) _4V=O]时，配合物在P4/ncc空间群中结晶。通过分子四折轴的分子间连接形成晶体四折轴，构成一维体系。由吡啶硫醇氧化生成的二硫化二吡啶被广泛用作生物测定试剂或合成物

In this research, the composite binuclear complex was prepared from [Pt (4-mpyt) _4] ^<2+> using the metal incorporating ability of this complex. The late transition metals as Ni (II) and Co (II) can be incorporated in this system with moderate yield. Both complexes have square planar structure for Pt (II), and tetragonal pyramidal either for Ni (II) and Co (II). The apical ligation to Co or Ni contribute for the stabilization of the system. Both complexes increase the inter metallic interaction upon oxidation to d^7-d^7 system, formally no apparent interaction present for the system. Especially, [Pt^<III> (4-mpyt) _4Co^<II>X] has strong inter metallic interaction causing diamagnetism as a result. The early transition metals can be incorporated in the form of its oxides as V=O or Cr=O.Especially, Cr (IV) has quite unique coordination sphere in this system that never happened in the mononuclear system. Furthermore, Cr (III) complex, [Pt (4-mpyt) _4Cr^<III>Cl], is surrounded by five ligating atoms with square pyramidal fashion that never appeared in Cr (III) state.The x-ray structural results show the evidence as follows. (1) Regardless of early or late, first transition metals can form [Pt (4-mpyt) _4MX] molecule. Four N atoms coordinate to first transition metals due to the hard metal preference compared to the soft S atoms. (3) In the case of [Pt (4-mpyt) _4Cr=O] or [Pt (4-mpyt) _4V=O], the complexes are crystallizes in the space group P4/ncc. As a result, the inter-molecular linkage through molecular 4 fold axis forms crystallographic 4 fold axis and making up the one dimensional system.Dipyridine disulfide formed by the oxidation of pyridine thiol is widely used as a bio assay reagent or the synthet