Development of New Organic Metals Based on TTF-Fused Donor Systems via "Complexation" of Organotin Compounds

我们发现TTF-稠合给体体系包括DHTTF-TTF、DTDT-TTF和DSDTF-TTF等新的给体体系的短步骤合成是通过Me_3Al促进的锡掩蔽的二硫纶与酯的反应实现的。从DHTTF-TTF给体出发，合成了10种新的金属电荷转移配合物和盐。特别地，对金属（EDDH-TTP）_2AuI_2盐（σ_<rt>= 14 S/cm）在4.2K下的X射线结构分析表明，EDDH-TTP是第一个产生κ型2：1盐的TTF稠合施主，许多有机超导体都是这种结构。尽管存在一个灵活的三亚甲基二硫代基团，DTDT-TTF稠合给体系统提供了七种新的分子基有机金属。此外，我们还成功地从DSDTF-TTF稠合给体中合成了四种新的有机金属化合物，并通过BF_3促进的锡二硫代酸盐与1，2-二卤杂环的反应，发展了一条通过多个杂环的加成得到一个新的具有扩展外围的TTF族化合物的合成路线。虽然这个新的TTF家族具有庞大的和非平面的结构，属于这个家族的二氧杂环己烷-，二噻烷-和二氧戊环附加的TTF衍生物已发现产生金属自由基阳离子盐。

We have found that the short-step synthesis of TTF-fused donor systems including new ones such as DHTTF-TTF,DTDT-TTF,and DSDTF-TTF fused donors is sffected via the Me_3 Al-promoted reaction of the tin-masked dithiolate and esters. Ten kinds of new metallic charge-transfer complex and salts could be cbtained from DHTTF-TTF donors. Particularly, an X-ray structure analysis of the metallic (EDDH-TTP)_2AuI_2 salt (sigma_<rt>=14S/cm) atable down to 4.2 K has revealed that EDDH-TTP is the first TTF-fused donor producing a kappa-type 2 : 1 salt ; note that many organic superconductors are of this structure. Despite the presence of a flexible trimethylenedithio group, the DTDT-TTF fused donor system provided seven kinds of new molecular-based organic metals. We have also succeeded in preparing four kinds of new organic metals from DSDTF-TTF fused donors.In addition, the synthertic route to a new TTF family with extended periphery by addition of several heterocycles has been developed via the BF_3-promoted reaction of tin dithiolates with 1,2-dihaloheterocycles. Although this new TTF family has a bulky and nonplanar structure, the dioxane-, dithiane-, and dioxolane-appended TTF derivatives belonging to this family have found to produce metallic radical-cation salts.