Pursuit of Synthesis and Functionality of the Materials Exhibiting Visible Fastener Effect

研究了中心金属和周围长链对不同长链取代双（二苯基乙氧嘧啶）金属配合物中形性和热致变色的影响。结果表明，这些长链取代的双（二苯基乙氧嘧啶）金属配合物不仅具有介晶性，而且具有“紧固件效应”引起的热致变色性。长链的种类和数量不仅影响着中晶结构，而且影响着热致变色的外观。结果表明，一维金属堆积结构对热致变色具有重要影响。结果表明，（C_nO） _8-Pt配合物在35℃时的“表观压力”为0.87GPa，且在n<或等于>12时，周围长链的紧固作用达到饱和平台。配体体积最大，金属离子最小的（C_<12>O） _8-Pt配合物对M=Ni, Pd， Pt表现出最强烈的热致变色，证实了这种热致变色是由M^<2+>离子的ndz^2- (n+1) pz带的蓝移引起的。这种可见的扣件效果，据我们所知，尚属首例。这必然是液晶有机金属配合物（metalomesogen）应用的新前沿。此外，即使仅在高压下表现出高电导率的化合物，我们也可以期望通过这种“紧固件效应”在大气压下获得高电子电导率。

The author investigated influences of the central metals and the surrounding long chains on mesomorphism and thermochromism of the various long chainsubstituted bis (diphenylglyoximato) metal complexes. It was revealed that these long chain-substituted bis (diphenylglyoximato) metal complexes exhibit not only the mesomorphic properties but also thermochromism caused by "fastener effect". The kinds and numbers of the long chains influence not only mesomorphic structures but also the appearance of thermochromism. It was revealed that the one-dimensional metal stacking structure crucially influences thermochromism. It was found that the value of "apparent pressure" is 0.87GPa for the (C_<12>O) _8-Pt complex at 35ﾟC,and that the fastener effect by the surrounding long chains attains to a saturated plateau for n<greater than or equal>12 in the series of the (C_nO) _8-Pt complexes. The (C_<12>O) _8-Pt complex which has the bulkiest ligand and the smallest metal ion exhibits the most drastic thermochromism among the (C_<12>O) _8-M complexes for M=Ni, Pd, Pt. It was confirmed that this thermochromism is caused by blue-shift of the ndz^2- (n+1) pz band of the M^<2+> ion. Such visible fastener effect is the first examples, so far as we know. This must be the new frontiers of application of liquid crystalline organic metal complexes (metallomesogen). In addition, we can expect to obtain high electronic conductivities by such "fastener effect" at atmospheric pressure even for the compounds exhibiting high conductivities only under high pressure.