Development of New Organic Superconductors based on Conducting Layr Designing

本文根据三种新颖的设计原则，对新型有机超导体的发展进行了研究，结果如下：1.设计阴离子层结构得到κ型ET配合物。本文研究了阴离子层NO_3 ~-与水分子连接的ET配合物的制备，得到了（ET）_2（NO_3）（H_2O）_2。该盐表现出了给体分子的rheta型堆积结构，并具有良好的电致发光性能，被认为是ET家族中罕见的Mott型半导体.增加导电层间的相互作用。本文研究了Ni（tdas）_2的金属配体体系，它在离子末端具有大的π电子密度。用OMTTF方法首次得到了该阴离子与TTF衍生物的晶体复合物，复合物中的分子完全电离，因此它是一种绝缘体。晶体结构类似于金属-二硫代草酸盐体系.形成厚导电层以增加有效导电空间。本文研究了一种新型导电组分对称取代BTDT分子的一般合成路线。这些衍生物具有两个与1，4-二噻烯的B和e位稠合的TTF部分。找到了关键中间体（2个1，3-二硫杂环戊烯-2-酮稠合的1，4-二硫杂环戊烯衍生物）的可重复合成方法。作为进一步的研究，我们合成了一系列具有相同形式电荷、不同尺寸的{RO-C [C（CN）_2] _2} ^-（R=正烷基），并制备了它们的导电配合物。此外，获得了其中供体分子被高度氧化的BEDO-TTF复合物。

The development of new organic superconductors have been investigated according to the three kinds of original designing principles which are listed in following with the results.1. Designing the Anion Layr Structure to give kappa-type ET Complexes. : The preparation of ET complex in which anion layr NO_3^- ions are linked by water molecules has been examined and (ET) _2 (NO_3) (H_2O) _2 was obtained. This salt showed the rheta-type packing motif of the donor molecules and semiconductive properties and was considered as a Mott type semiconductor which is rare in ET family.2. Increasing the Inter-Conducting-Layr Interactions. : A metal-ligand system of Ni (tdas) _2 which shows the big pi-electron densities at the terminals of the ion has been examined. The first crystalline complex of this anion and TTF derivatives was obtained using OMTTF.The component molecules are completely ionized in this complex and hence it is an insulator. The crystal structure resembles to that of metal-dithiaoxlate system.3. Formation of Thick Conducting Layr to Increase the Effective Conducting Space. : The general synthetic route of a new conducting component molecule of symmetrically substituted BTDT has been investigated. These derivatives have two TTF moieties fused to the b and e positions of 1,4-dithiine. The reproducible synthetic method of the key intermediate (the 1,4-dithiine derivative to which two 1,3-dithiole-2-thione are fused) was found out. The optimization of the reaction condition and the identification of the target BTDT's are under way, at present.As the additional investigation, a series of {RO-C [C (CN) _2] _2} ^- (R=n-alkyl) which have the same formal charge and different sizes have been synthesized and their conducting complexes have been prepared. Also, the BEDO-TTF complexes in which the donor molecules are highly oxidized were obtained.