Creation of conductive supramolecular frameworks tailored by anisotropic intermolecular interactions and development of multi-functional materials

这一点是众所周知的，因为有机导体中晶体和电子结构的变化不仅取决于单个分子结构，但也取决于晶体中的分子排列。We have proposed the introduction of strong and directional I... N type intermolecular interactions （“iodine bond”） to organic conductors for the sake of cr？engineering. i） The known method for the syntheses of TTF-vinylogues based on the Wittig-type reaction includes multi-step syntheses of the starting materials。我们为碘键的TTF-乙烯基合成开发了一种新的和简单的方法。这一直接对Thione和Aldehyde的反应是对替代品的轻微无管制。We have obtained a series of novel iodine-bonded TTF-vinylogues. ii）在iodine-bonded diselenedithiafulvalene "DIPS" has been studied。The channel structure is similar to those of the inorganic "zeolite"\and it would be promising to introduce a variety of guest molecules to obtain multi-functional materials. iii） We have prepared a novel supramoleeular organic conductor（DIETS）2[Au（CN）_4] and measured the temperature dependence of the electrical resistence under the uniaaxial Management in。超导电性过渡约为10千巴，超导电性的初始温度达到8 K。这是基于已知的超级导体（π-donors）上的最高记录。Furthermore，独特的应变显示出较大的异源性的影响（iv）我们已经准备好了一种不使用高毒性试剂H_2Se和CSe_2的碘结合四氮氟乙烯（TSeF）衍生物。一种新的有机导体（DIETSe）>2AuCl_2的金属含量降低到4.2 K，其房间温度调节提高到700 Scm<-1>。X射线结构分析已经揭示，独特的超分子结构已经由I... CI和l... Au strong碘键开发。

It is well known that the variety of crystal and electronic structures in organic conductors depends not only on the structure of an individual molecule but also on the molecular arrangement in the crystal. We have proposed the introduction of strong and directional I・・・N type intermolecular interactions ("iodine bond") to organic conductors for the sake of crystal engineering.i) The known method for the syntheses of TTF-vinylogues based on the Wittig-type reaction includes multi-step syntheses of the starting materials. We have developed a new and simple method for the synthesis of iodine-bonded TTF-vinylogues. This direct coupling reaction of thione and aldehyde proceeds smoothly regardless of the substituent. We have obtained a series of novel iodine-bonded TTF-vinylogues.ii) Thermal behavior of a unique hexagonal system based on the iodine-bonded diselenedithiafulvalene "DIPS" has been studied. The channel structure is similar to those of the inorganic "zeolite" systems and it would be promising to introduce a variety of guest molecules to obtain multi-functional materials.iii) We have prepared a novel supramoleeular organic conductor θ-(DIETS)2[Au(CN)_4] and measured the temperature dependence of the electrical resistivity under the uniaxial strain. Superconducting transition was observed around 10 kbar and the onset temperature of the superconductivity has reached 8 K. It is the highest record among the known superconductors based on unsymmetrical organic π-donors. Furthermore, the effect of the uniaxial strain showed large anisotropy as expected.iv) We have prepared iodine-bonded tetraselenafulvalene (TSeF) derivatives without the use of highly toxic reagents H_2Se and CSe_2. A new organic conductor (DIETSe)>2AuCl_2 is metallic down to 4.2 K and its room temperature conductivity is up to 700 Scm<-1>. X-ray structure analysis has revealed that the unique supramolecular structure has been developed by the I・・・CI and l・・・Au strong iodine bond.