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A Synthetic Approach to the Ferroelectric Metallomesophase Materials Utilizing the Polarity of Coordinate Bonds

利用配位键极性合成铁电金属中间相材料的方法

基本信息

批准号：
06453045
负责人：
MIYAJIMA Naomi
金额：
$ 4.74万
依托单位：
HOKKAIDO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1996
项目状态：
已结题

项目摘要

A synthetic research has been undertaken in order to develop ferroelectric metallomesophase materials utilizing the polarity of coordinate bonds. Three types of complexes were chosen for the study and the mechanism of possible dipolar ordering in metallomesophases has been assessed.1. On the Formation of Smectic C Phases by Metal-salicylaldimine Complexes and the Effect of Dipolar Interactions. A straightforward approach to the ferroelectric liquid crystals is to prepare chiral smectic C materials. In need of understanding the molecular origin for tilted smectics in the first place, a wide variety of copper-salicylaldimine mesogens have been analyzed in this study for their mesomorphic characteristics, the smectic A/C polymorphism in particular. The results suggest that the dipole density wave should be controlled to be commensurate with the one-dimensional positional order if we are to stabilize the tilted phase.2. On the Smectic Mesomorphism in Metal-dithiocarbamate Complexes anda Ch … More iral Modification. The metal-dithiocarbamate complexes have been designed in order to obtain a metallomesogen, molecular shape of which can be viewed as simply rodlike, and test applicability of existing molecular theories. A new group of smectic C materials have been obtained, and a chiral derivative with a methyl tail-branching is now in hand.3. On the Mesomorphism of Complexes of [M (salen) ] Type. The goal of this study has been to achieve a direct interaction between polarized coordinate bonds such as one in metal-oxo group, leading to the ferroelectric ordering. Such mechanism has been proposed in the literature on oxovanadium omplexes of salen derivatives. However, formation of centrosymmetric dimeric aggregates has been hinted in the present study on their nickel and copper analogues. This may be a widespread problem in metallomesogens of low molecular symmetry and carrying strongly polarized bonds. It seems that the ligand design needs to be elaborated further if we are to control the mesomorphic and the dipolar ordering behaviors. Less

为了开发利用配位键极性的铁电金属食道材料，人们进行了一项综合研究。选择了三种类型的络合物进行研究，并对金属食道中可能的偶极有序化机理进行了分析。金属-水杨醛二胺络合物形成近晶C相及偶极相互作用的影响制备手性近晶C材料是制备铁电液晶的一种直接方法。为了首先了解倾斜近晶的分子起源，本研究分析了各种铜-水杨醛二胺介晶的介晶特征，特别是近晶A/C多态。结果表明，若要使倾斜相稳定，偶极密度波应控制在与一维位序相称的位置。金属-二硫代氨基甲酸酯络合物和CH-…的近晶介晶化更多的病毒修改。金属-二硫代氨基甲酸酯络合物的设计是为了获得一种分子形状可以简单地视为棒状的金属成因，并检验现有分子理论的适用性。得到了一组新的近晶C材料，并合成了一种具有甲基尾部支化的手性衍生物。关于[M(Salen)]型络合物的介晶性这项研究的目标是实现极化配位键之间的直接相互作用，如金属-氧代基团中的一个，从而导致铁电有序。在关于Salen衍生物的氧钒络合物的文献中已经提出了这样的机制。然而，目前对它们的镍和铜类似物的研究表明，形成了中心对称的二聚体聚集体。这可能是低分子对称性和带有强极化键的金属成因中普遍存在的问题。看来，如果我们要控制介晶和偶极有序化行为，配体的设计还需要进一步细化。较少