Conjugated Assembly of Viologens with Spin Manipulation

利用自旋操作共轭组装紫罗碱

• 批准号: 11305061
• 负责人: IYODA Tomokazu
• 金额: $ 23.83万
• 依托单位: Tokyo Metropolitan University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11305061/
• 关键词: Photoelectrochemical Control; Spin Functional Unit; Conjugated Assembly; Conjugated Polyviologen; Redox-active Ligand; Photo-induced Electron Transfer in Crystal; Log-satcking Structure; Photo-Induced Radical Pair; スピン機能単位; 全共役ポリビオローゲン; レドックス制御

Multi-step redox processes are reported in several it-conjugated assemblies of photoelectrochemically active pyridinium units, leading to function-integrated molecular assembly. The strategy has been set to strongly link each redox active unit and then to understand the correlated redox properties, (1) The arylene-linked viologen dimers showed four-step reduction processes in which mono-radical, triplet diradical, half and full quinoid structures are controlled photoelectrochemically. (2) The coordination assembly of bidentate pyridyl pyridinium ligands with paramagnetic metal ions exhibited photochemically tunable spin ordering through antiferromagnetic coupling of the intervening pyridyl radicals. (3) The d-π-dependent multi-step redox processes were demonstrated in various bis(pyridinio)-β-diketone metal complexes, together with their discotic columnar structures. The interaction path analysis giving a guideline for the coming molecular devices with electronic communication will be discussed. Interestingly, triplet ground state was confirmed in inter-ligand trans-configuration and intra-ligand configuration of two pyridinylradicals, while the inter-ligand cis-configuration was thermally excited triplet state, i.e., singlet biradical in the ground state. The electrochemical control of both geometric and electronic structures of the helical conjugated polymers will be also introduced by precisely fabricating pyridinium units in poly (arylisocyanide). Additionally, new modification of conducting polymers will be also introduced by anodic nucleophilic substitution of pyridine derivatives. Remarkable progress has been made in the study of well-designed coordination polymers to take the major place in supramolecular chemistry, which is providing various kinds of nano-structures, in several-to-decades nanometer scales, by self-assembly of small building blocks.

多步氧化还原过程被报道在几个光电化学活性吡啶单元的it共轭组装中，导致功能集成的分子组装。该策略被设定为将每个氧化还原活性单元紧密联系在一起，然后了解相关的氧化还原性质：(1)芳烃连接的紫精二聚体表现出四步还原过程，其中单自由基、三重双自由基、半和全奎宁结构受光电化学控制。(2)双齿吡啶配体与顺磁性金属离子的配位组装通过中间吡啶自由基的反铁磁耦合表现出光化学可调谐的自旋有序性。(3)在不同的双(吡啶)-π-二酮金属络合物及其盘状柱状结构中，存在依赖d-β的多步氧化还原过程。将讨论相互作用路径分析，为未来的电子通信分子器件提供指导。有趣的是，在两个吡啶自由基的配体间反式构型和配体内构型中确认了三重基态，而配体间顺式构型是热激发三重态，即基态中的单重态双自由基。通过在聚芳基异氰酸酯中精确制备吡啶单元，还将介绍对螺旋共轭聚合物几何结构和电子结构的电化学控制。此外，还将通过对吡啶衍生物的阳极亲核取代来引入导电聚合物的新的改性。设计合理的配位聚合物在超分子化学中占据重要地位的研究已经取得了显著的进展，它通过小块的自组装提供了各种纳米结构，在几十到几十纳米尺度上。

项目成果

Jie Zhang, M.M.Matsushita, X.X.Kong, Jiro Abe, Tomokazu Iyoda: "Photo-responsive Coordination Assembly with a Versatile Logs-stacking Channel Structure Based on Redox-active Ligand and Cupric Ion"J. Am. Chem. Soc.. 123(48). 12105-12106 (2001)

张杰，M.M.Matsushita，X.X.Kong，Jiro Abe，Tomokazu Iyoda：“基于氧化还原活性配体和铜离子的多功能原木堆积通道结构的光响应配位组装”J。

Zhong-Ze Gu, Tomokazu Iyoda, Akira Fujishima, Osamu Sato: "Photo-Reversible Regulation of Optical Stop Bands"Adv. Mater.. 13(17). 1295-1298 (2001)

顾忠泽、Tomokazu Iyoda、Akira Fujishima、Osamu Sato：“光阻带的光可逆调节”Adv.

Z.-Z. Gu, O. Sato, Y. Einaga, M. Kai, I Iyoda, A. Fujishima, K. Hashimoto: "Crystal Structure and Photo-reaction of a new Coordination Polymer : [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]・6H2O"Bull. Chem. Soc. Jpn.. 74. 1617-1622 (2001)

Z.-Z. Gu、O. Sato、Y. Einaga、M. Kai、I Iyoda、A. Fujishima、K. Hashimoto：“新型配位聚合物的晶体结构和光反应：[Ni(en)2] 4[Fe(CN)5NO]2[Fe(CN)6]・6H2O"Bull. Chem. Soc. Jpn.. 74. 1617-1622 (2001)

松下未知雄,彌田智一 他3名: "Intramolecular Magnetic Interaction of Phenylene-linked Bis-beta-diketone Metal Complexes"Chem.Lett.. 2000. 812-813 (2000)

Michio Matsushita、Tomokazu Yata 等 3 人：“亚苯基连接的双-β-二酮金属络合物的分子内磁相互作用”Chem.Lett.. 2000. 812-813 (2000)

Tadashi KAWAI, Masako KOMAKI, Tomokazu IYODA: "Cross-metathesis of vinyl aromatic heterocycles : Comparison of Grubbs catalsyt and Schrock catalyst"J.Mol.Catalysis A. (印刷中). (2002)

Tadashi KAWAI、Masako KOMAKI、Tomokazu IYODA：“乙烯基芳族杂环的交叉复分解：Grubbs 催化剂和 Schrock 催化剂的比较”J.Mol.Catalysis A.（出版中）。