Synthetic Study of Oligomeric TTF-Superphanes Expectative to Form Supramolecular Assemblies

寡聚 TTF-Superphanes 的合成研究，有望形成超分子组装体

• 批准号: 13640569
• 负责人: KAWADA Yuzo
• 金额: $ 2.24万
• 依托单位: IBARAKI UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640569/
• 关键词: TTF; macrocyclic compound; super phane; X-ray analysis; Electro-crystallization; twin donor

TTF superphanes in which three or four TTF skeletons are connected by either two ethylendithio or two propanedithio bridges were designed and their syntheses have been tried.They have unique shapes, the former being a prism, the latter being a square pillar, and are expected to self-assemble hexagonal and tetragonal units, respectively through face-to-face πinteractions, which, in turn, to form columnar assemblies equipped with extended channel Structures through edge-to-edge S-S contacts.In spite of many synthetic difficulties, which were mainly due to poor solubilities of various intermediates, two kinds of precursor to the trimer have been prepared. In one, three TTF moieties are connected by totally four propanedithio groups and the two TTF moieties at both sides have two protected thiol groups. Deprotection followed by the reaction with 1,3-dibromopropane was expected to give the trimer. In the other, two TTFs and two 1,3-dithiole-2-0ne are connected and deoxygenative coupling should give the target.The two reactions have been carried out under various conditions and always under high-dilution conditions to give, in some cases, extremely small amount of the target discernible only through TOFMS. Further elaboration of the reaction conditions are in progress.

设计并尝试了由两个乙二硫桥或两个丙二硫桥连接三个或四个TTF骨架的TTF超芬胺，它们具有独特的形状，前者为棱柱，后者为方柱，有望通过面对面的π相互作用，分别自组装六边形和四边形单元，进而形成配备扩展通道结构的柱状组件尽管存在许多合成困难，主要是由于各种中间体的溶解性差，但还是制备了两种三聚体前体，其中三个TTF部分由总共四个丙二硫基团连接。两侧的两个 TTF 部分都有两个受保护的硫醇基团，然后与 1,3-二溴丙烷反应预计会产生三聚体。两个1,3-二硫醇-2-0ne连接，脱氧偶联应得到目标产物。这两个反应在各种条件下进行，并且总是在高稀释条件下进行，在某些情况下，得到极少量的只能通过 TOFMS 辨别目标。反应条件的进一步阐述正在进行中。

项目成果

A.Izuoka, J.Tanabe, T.Sugawara,^* T.Kudo, T.Saito, and Y.Kawada,^*: ""Charge Transfer Assisted Ferromagnetic Coupling Observed in An lon-Radical Salt of a Cross-Cyclophane TTF-Based Donor""Chem. Lett.. 910-911 (2002)

A.Izuoka、J.Tanabe、T.Sukawara、^* T.Kudo、T.Saito 和 Y.Kawada，^*：“在跨环烷 TTF 的长自由基盐中观察到的电荷转移辅助铁磁耦合”

J.Nakazaki, I-G.Chung, R.Watanabe, T.Ishitsuka, Y.Kawada, M.M.Matsushita, and T.Sugawara^*: ""Design of Spin-Polarized Molecular Wire as a PrototypalUnimolecular Quantum Spin Device""Internet Electron. J. Mol. Design. 1 (2002)

J.Nakazaki、I-G.Chung、R.Watanabe、T.Ishitsuka、Y.Kawada、M.M.Matsushita 和 T.Sugarara^*：“作为原型单分子量子自旋器件的自旋极化分子线的设计”“互联网电子。

中崎城多郎 他: "Charge Transfer Assisted Ferromagnetic Coupling Observed in An Ion-Radical Salt of a Cross-Cyclophane TTF-Based Donor"Chem. Lett.. 910-911 (2002)

Jotaro Nakazaki 等人：“在基于交叉环烷 TTF 的供体的离子自由基盐中观察到的电荷转移辅助铁磁耦合”Chem. 910-911 (2002)

J.akazaki, I-G.Chung, M.M.Matsushita, T.Sugawara,^* R.Watanabe,A.Izuoka, and Y.Kawada: ""Design and Preparation of Pyrrole-Based Spin-Polarized Donors""J. Mater. Chem.. in press.

J.akazaki、I-G.Chung、M.M.Matsushita、T.Sukawara、^* R.Watanabe、A.Izuoka 和 Y.Kawada：“基于吡咯的自旋极化供体的设计和制备”J.

泉岡明他5名: "Charge Transfer Assisted Ferromagnetic Coupling Observed in An Ion-Radical Salt of a Cross-Cyclophane TTF-Based Donor"Chem. Lett.. 910-911 (2002)

Akira Izuoka 等 5 人：“在基于交叉环芳 TTF 的供体的离子自由基盐中观察到的电荷转移辅助铁磁耦合”Chem. 910-911 (2002)