Development of New Organic Superconductors based on Conducting Layr Designing

根据这三种原创设计原则，对新型有机超导体的发展进行了研究。设计阴离子层结构以得到kappa类型的ET络合物。本文研究了以水分子连接硝酸根阴离子的ET络合物的制备，得到了(Et)_2(NO_3)(H_2O)_2。该盐表现出施主分子的Rheta堆积基序和半导体性质，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，该体系在离子的末端显示出较大的pi电子密度。利用OMTTF得到了该阴离子与TTF衍生物的第一个结晶络合物，其组成分子在该络合物中完全电离，因此它是一种绝缘体。其晶体结构类似于金属-二硫代氧酸盐体系。形成厚的导电层以增加有效导电层。研究了一种新型对称取代BTDT导电组分分子的合成路线。这些衍生物有两个TTF部分融合在1，4-二硫杂环的b和e位上。找到了关键中间体1，4-二硫杂衍生物(两个1，3-二硫杂环-2-硫酮熔合而成)的重复性合成方法。目前，反应条件的优化和目标BTDT的鉴定正在进行中，作为补充研究，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=n-烷基)，并制备了它们的导电络合物。此外，还得到了给体分子高度氧化的Bedo-TTF络合物。

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.