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

为了开发利用配位键极性的铁电金属相材料，进行了一项综合研究。选择了三种类型的配合物进行研究，并对金属相中可能的偶极有序机制进行了评估。金属-水杨醛二胺配合物形成近晶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，本研究分析了多种铜-水杨醛二胺中晶的近晶特征，特别是近晶a /C多态性。结果表明，要稳定倾斜相位，必须控制偶极子密度波，使之与一维位置顺序相适应。金属-二硫代氨基甲酸酯配合物的同形性及更多病毒修饰。设计了金属-二硫代氨基甲酸酯配合物，以获得分子形状可视为简单棒状的金属合成源，并测试了现有分子理论的适用性。获得了一组新的近晶C材料，并得到了一种具有甲基尾支的手性衍生物。[M (salen)]型复合体的中胚性。本研究的目标是实现极化配位键之间的直接相互作用，例如金属-氧基中的一个，从而导致铁电有序。这一机理已在salen衍生物的氧钒配合物的文献中提出。然而，在目前对它们的镍和铜类似物的研究中暗示了中心对称二聚体聚集体的形成。这可能是在低分子对称性和携带强极化键的金属合成源中普遍存在的问题。因此，若要控制介态和偶极序行为，配体的设计还需进一步完善。少

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