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

通过有机锡化合物的“络合”开发基于 TTF 融合供体系统的新型有机金属

• 批准号: 08640694
• 负责人: YAMADA Jun-ichi
• 金额: $ 1.47万
• 依托单位: Himeji Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08640694/
• 关键词: Organotin Compounds; Complexation; New TTF-Fused Donor Systems; New Organic metals; Trimethylaluminium; kappa-Type; Heterocycles; Boron Trifluoride; エステル; 金属的錯体; 構造解析; 物性

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.

我们发现，TTF-熔融施主体系包括DHTTF-TTF、DTDT-TTF和DSDTF-TTF等新型给电子体的短步合成是通过Me_3Al促进的二硫代锡和酯类化合物的反应实现的。从DHTTF-TTF给体中可以得到10种新的金属电荷转移络合物和盐。特别是，金属(EDDH-TTP)_2AuI_2盐(Sigma_&lt；RT&gt；=14s/cm)的X射线结构分析表明，EDDH-TTP是第一个产生kappa-type 2：1盐的TTF-熔融施主；注意，许多有机超导体都具有这种结构。尽管存在一个灵活的三亚甲基二硫基团，DTDT-TTF融合供体系统仍提供了七种新的分子基有机金属。我们还成功地从DSDTF-TTF熔融供体中合成了四种新的有机金属。此外，通过BF_3促进的二硫代锡与1，2-二卤代杂环的反应，我们还开发了通过添加几个杂环来合成具有扩展外围的TTF家族的合成路线。虽然这个新的TTF家族有一个庞大的非平面结构，但属于这个家族的二恶烷、二硫杂环和二氧杂环戊烷的TTF衍生物已经被发现可以产生金属自由基阳离子盐。

项目成果

J. Yamada: "Radical Cation Salts Based on TTF (s) -DHTTF (Dihydrotetrathiafulvalene) Fused Donors : Electrical Conductivities…" J. Chem. Soc., Chem. Commun.2517- (1996)

J. Yamada：“基于 TTF (s) -DHTTF（二氢四硫富瓦烯）融合供体的自由基阳离子盐：电导率……”J. Chem.，Chem.2517- (1996)

J.Yamada: "Synthesis of Unsymmetrical Tetrathiafulvalene Derivatives via Me_3Al-Promoted Reactions of Organotin Compounds with Esters" J.Org.Chem.61. 3987-3995 (1996)

J.Yamada：“通过 Me_3Al 促进的有机锡化合物与酯的反应合成不对称四硫富瓦烯衍生物”J.Org.Chem.61。

S.Uji: "Temperature and Magnetic Field Dependences of Rapid Oscillations in Field Induced Spin-Density-Wave Phase for(TMTSP)_2ClO_4" Synth.Met.86. 1909-1910 (1997)

S.Uji：“(TMTSP)_2ClO_4 场感应自旋密度波相位中快速振荡的温度和磁场依赖性”Synth.Met.86。

S.Uji: "ORIGIN OF RAPID OSCILLATION IN THE METALLIC PHASE FOR THE ORGANIC CONDUCTOR(TMTSF)_2ClO_4" Solide State Commun.103. 387-392 (1997)

S.Uji：“有机导体金属相快速振荡的起源（TMTSF）_2ClO_4”固态Commun.103。

J.Yamada,: ""New Organic Metals Based on a BEDT-TTF Derivative with Steric Hindrance"" J.Mater.Chem.,. 7. 1311-1312 (1997)

J.Yamada，：“基于具有空间位阻的 BEDT-TTF 衍生物的新型有机金属”，J.Mater.Chem.，。