種々のホモイオンモンモリロナイトと４．４′‐メチレン‐ビス‐（２‐クロロアニリン）とのコンプレックス

Eleven homoionic montmorillonites were subjected to form complexes with an amine possesing two aromatic rings of chloroaniline type connected through a central methylene bridge in a bent form. The amine is 4, 4'-methylene-bis-(2-chloroaniline). The complexes obtained showed various noticeable features depending on preparation ways and interlamellar ion species, as in the following:(1) the complexes resulted by immersing montmorillonites saturated with H⁺, Ca²⁺, Sr²⁺, Mg²⁺, Zn²⁺, Cd²⁺, Mn²⁺, Fe³⁺, Cu²⁺, Co²⁺ and Ni²⁺ in acetone solution of the amine respectively gave 14-15A of d (001) and almost same light reddish purple colors, indifferently with respect to the ion species;(2) in contrast to (1), complexes made by immersing the same montmorillonites in a melt of the amine at ca. 140°C do show marked differences in the features suggesting the formation of different assemblages between the clay sheets, viz. only four montmorillonites saturated with Mn²⁺, Fe³⁺, Co²⁺ and Cu²⁺ can yield complexes which give rise to the basal spacing of at least 20 Å and show their own colors (dark carmine, brown, dark reddish brown and black corresponding the employment of Mn²⁺, Fe³⁺, Co²⁺ and Cu²⁺ respectively), whereas, other substitution clays formed complexes which give 14-15Å of d (001), similarly as the case of (1), however, their colors were not the light but dull brown mostly.<BR>Here, it is noted that the four ion species as mentioned above are transition metal ions having odd number electrons in their d-shell without exception, and that the magnitude of the interlayer clearance in the long-periodicity complexes can agree with approximately a long-axis spacing of the amine molecule and twice of the short-axis spacing.<BR>Then, the assemblage configurations between the sheets were conjectured in the light of the X-ray data and pronounced inactive properties of the amine per se for oxydations and for solutional complex formations with all ions used.<BR>Here, concerning the conjectures, the present authors are possesed with a perceiving that interactions of the amine-aromatic π electron for the metallic ions in wide meanings, might sensibly be taken into account. And in this, not only the π electron coordination but also the electro-static interactions between the organic molecule and the cations should be worth considerations particularly when it was thought that the rather high temperature of the amine-melt did effectively removed interlayer hydration water, and consequently that electric fields between the cations and clay sheets of negatively charged should draw the ring π electron toward the. mid-way position cations.