Correlation between structures and physical properties for pi-conjugated multinuclear complexes

π共轭多核配合物的结构与物理性质之间的相关性

• 批准号: 09440226
• 负责人: NISHIHARA Hiroshi
• 金额: $ 7.87万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440226/
• 关键词: pi-conjugation; multinuclear complex; electronic interaction; mixed-valence state; electrochemistry; ferrocene; dithiolene complex; terpyridine complex; アゾ; π供役; レドックス; ジチオラト錯体; 金属クラスター錯体

In the research of 7t-conjugated multinuclear transition metal complexes, it is important to investigate the correlation between structures and strength of intermuclear electronic interactions with physical properties. In this study, we have synthesized new oligomeric and polymeric compounds involving ferrocene, cobaltadithiolene and terpyridine complexes, and investigated the correlation between their structures and redox, optical and magnetic properties.New azo-bridged ferrocene trimers, Fc-Fc'-N=N-Fc and Fc-N=N-Fc'-N=N-Fc, where Fc and Fc' refer to (eta^5-C_5H_5)Fe(eta^5-C_5H_4-) and Fe(eta^5-C_5H_4-)_2, respectively, were synthesized. Their electrochemical and optical properties indicate that the electronic structures of their mixed-valence states can be expressed as Fc^+-N_2-Fc'-N_2-Fc, Fc^+-N_2-Fc'-N_2-Fc^+, and Fc^+-Fc'-N_2-Fc, Fc^+-Fc' -N_2-Fc^+, respectively. The solvent effect of the IT band in their mixed-valence states on nu_<max> cannot be interpreted only by the parameter … More s in the Marcus-Hush theory, indicating that the nature of the solvent as donor or acceptor should be taken into account in the electron-exchange process in the mixed-valence states.Redox properties and optical properties of o, m, and p-bis (ferrocenylethynyl) benzene indicate that the electronic interaction between ferrocene units is most significant when they locate at para position. Physical properties of hexaxis (ferrocenylethynyl) benzene can be semi-quantitatively interpreted by considering the contribution of all electronic interaction between ferrocene units at o, m and p-positions.New Co-M-Co (M=Mo, W) cluster complexes were synthesized by the reaction of cobaltadithiolene complex with M(CO)_3py_3 and their X-ray crystallographic structures determined. Physical properties of them and their reduced forms indicate the existence of strong electronic interaction between two Co sites via the central metal.A new bis (terpyridine) ligand with azobenzene as the linker, tpy-AB-tpy and their Rh, Ru and Co dinuclear complexes were synthesized. Their photoisomerization reactions and redox properties were revealed. Less

在7t共轭多核过渡金属配合物的研究中，研究核间电子相互作用的结构和强度与物理性质之间的关系是非常重要的。在本研究中，我们合成了新的二茂铁、钴二硫烯和三联吡啶配合物的低聚物和聚合物，并研究了它们的结构与氧化还原、光学和磁性能的关系。合成了新的偶氮桥接二茂铁三聚体Fc-Fc'- n =N-Fc和Fc- n =N-Fc‘- n =N-Fc，其中Fc和Fc’分别表示（eta^5-C_5H_5）Fe（eta^5-C_5H_4-）和Fe(eta^5-C_5H_4-)_2。电化学和光学性质表明，它们混合价态的电子结构可分别表示为Fc^+-N_2-Fc'-N_2-Fc, Fc^+-N_2-Fc'-N_2-Fc^+, Fc^+-Fc'-N_2-Fc ^+, Fc^+-Fc'-N_2-Fc ^+。混合价态的IT能带对nu_<max>的溶剂效应不能仅用Marcus-Hush理论中的参数…More s来解释，这表明在混合价态的电子交换过程中，溶剂作为供体或受体的性质应加以考虑。o、m和p-双（二茂铁乙基）苯的氧化还原性质和光学性质表明，当二茂铁单元位于对位时，它们之间的电子相互作用最显著。六轴（二茂铁乙炔基）苯的物理性质可以通过考虑o、m和p位二茂铁单元之间所有电子相互作用的贡献来半定量地解释。用钴二硫烯配合物与M(CO)_3py_3反应合成了新的CO -M- CO （M=Mo， W）簇状配合物，并测定了其x射线晶体结构。它们的物理性质及其简化形式表明两个Co位点之间通过中心金属存在强电子相互作用。合成了一种以偶氮苯为连接体的新型双（三联吡啶）配体tpy-AB-tpy及其Rh、Ru和Co双核配合物。揭示了它们的光异构化反应和氧化还原性质。少

项目成果

I.Matsuoka, K.Aramaki, H.Nishihara: "Regioselective Synthesis and Electrochemical Properties of pi-Conjugated Cobaltacyclopentadiene Oligomer and Polymer Complexes" J.Chem.Soc., Dalton Trans.1998 (1). 147-152

I.Matsuoka、K.Aramaki、H.Nishihara：“π-共轭钴环戊二烯低聚物和聚合物复合物的区域选择性合成和电化学性质”J.Chem.Soc.，Dalton Trans.1998 (1)。

H.Nishihara: "Organaometallic Conductive Polymers In Handbook of Organic Conductive Molecules and Polymers, ed by H.S.Nalwa" Wiley, Chichester Chapter 19. 799-832 (1997)

H.Nishihara：“有机导电分子和聚合物手册中的有机金属导电聚合物，由 H.S.Nalwa 编辑”Wiley，奇切斯特第 19 章。799-832 (1997)

M.Nihei, T.Nankawa, M.Kurihara, H.Nishihara: "), a Novel" Angew.Chem.Int.ED.Engl.(in press). (1999)

M.Nihei、T.Nankawa、M.Kurihara、H.Nishihara：“），一部小说”Angew.Chem.Int.ED.Engl.（印刷中）。

M.Okuno, K.Aramaki, H.Nishihara: "Simulation of Change in Conproportionation Constants of the Windmill Complex,【Cp_3 Co_3(S_6 C_6)^<n->】in the Mixed-Valence States (n=1,2),by Addition of Crown Ethers to Solutions of Alkaline Metal Ions." J.Electroanal.Che

M.Okuno，K.Aramaki，H.Nishihara：“风车复合体的比例常数变化的模拟，【Cp_3 Co_3(S_6 C_6)^<n->】在混合价态（n=1,2） ，通过将冠醚添加到碱金属离子溶液中。”J.Electroanal.Che

M.Okuno,K.Aramaki,H.Nishihara: "Simulation of Change in Conproportionation Constants of the Windmill Complex, [Cp_3Co_3(S_6C_6)]^<n+> in the Mixed-Valence States (n=1,2),by Addition of Crown Ethers to Solutions of Alkaline Metal Ions." J.Electroanal.Chem.

M.Okuno、K.Aramaki、H.Nishihara：“通过加法模拟风车复合体的配比常数变化，[Cp_3Co_3(S_6C_6)]^<n > 在混合价态 (n=1,2)