Synthesis and Molecular Design of Ruthenium Polynuclear Complexes Responding Logically to Trigger Signals

逻辑响应触发信号的钌多核配合物的合成和分子设计

• 批准号: 06804036
• 负责人: HAGA Masaaki
• 金额: $ 1.34万
• 依托单位: Mie University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06804036/
• 关键词: Ruthenium polynuclear complexes; Molecular switching; Proton; Intramolecular electron transfer; ルテニウム錯体; 多核錯体; 光誘起電子移動; プロトン移動; スイッチング

We are focusing on the molecular design of the Ru polynuclear complexes which can respond logicaly to the trigger signal such proton movements. The summary of this project during the term is the following :(1) Synthesis of Ru di- and tetranuclear complexes bridged by organice benzimidazole. We have developed the chemical principle underlying the proton-induced switching of redox potential, i.e., reversible protonation of uncoordinated nitrogen site in 2- (2-pyridyl) benzimidazole Ru di- and tetranuclear complexes. In heteronuclear Ru-Rh dinuclear complex, the emission was observed at the deprotonated state of Rh site, however when the protonation occurred at Rh site, no emission was observed. Thus, the emission switching was observed in this dinuclea complex. We are extending this chemistry to the dendrimer type tetranuclear complexes. Two oxidation patterns have been reported in ligand-bridged dendrimer tetranuclear complexes when the four metal ions are connected by bridging ligands … More in the star-burst like manner and each metal-metal interaction is weak. Pattern A consists in simultaneous oxidation of three peripheral metals at almost same potentials prior to one-electron oxidation of the central metal ion. The second pattern B is the reverse. In the present RuOs mixed metal tetranuclear complex, [ {Os (bpy)_2 (bbbpyH_2) }_3 Ru] (CIO_4)_8 (bpy=2,2'-bipyridine) , the two redox patterns A and B can be interchanged by protonation of basic sites. Within the one-electron oxidized form of the deprotonated complex 2^+ (Ru^<III>Os^<II>_3) , the electron transfer from peripheral Os^<II> to central Ru^<III> moiety has occurred on protonation.(2) Formation of photoinduced charge separated state in RuOs Complex : The picosecond laser flash photolysis of dinuclear Ru (II) -NDI-Os (III) complex shows that the bleaching of MLCT band and then the appearance of new bands at 650 nm were observed. These new bands corresponds to the fprmation of Ru (III) -NDI-Os (II) state. The stepwise photoinduced electron transfer from the Ru (bpy) moiety to the dicarboximide, and then Os (III) occurred.(3) We showed that electrospray ionization mass spectra is a powerful tool for the characterization and purity check of tetranuclear Ru complexes. Less

我们致力于钌多核配合物的分子设计，这些配合物可以逻辑地响应质子运动等触发信号。本课题的主要内容如下：（1）有机苯并咪唑桥联的钌双核和四核配合物的合成。我们已经发展了质子诱导的氧化还原电位转换的化学原理，即，2-（2-吡啶基）苯并咪唑钌双核和四核配合物中非配位氮位的可逆质子化。在Ru-Rh双核配合物中，在Rh位去质子化时观察到发射，而当Rh位质子化时，没有观察到发射。因此，在这种双核复合物中观察到发射开关。我们正在将这种化学方法扩展到树枝状聚合物类型的四核配合物。在配体桥联的树枝状大分子四核配合物中，当四种金属离子通过桥联配体连接时，已经报道了两种氧化模式 ...更多信息 以类似于恒星爆发的方式，并且每个金属-金属相互作用都很弱。模式A包括在中心金属离子的单电子氧化之前，在几乎相同的电势下同时氧化三种外围金属。第二种模式B则相反。在本研究的RuOs混合金属四核配合物[ {Os（bpy）_2（bbbpyH_2）}_3Ru]（ClO_4）_8（bpy= 2，2 '-bipyridine）中，两种氧化还原模式A和B可以通过碱性位的质子化而互换。在去质子化的单电子氧化形式的配合物2^+（Ru^<III>Os^<II>3）中，电子从外围的Os^转移<II>到中心的Ru^<III>部分发生质子化。(2)RuOs配合物中光生电荷分离态的形成：双核Ru（II）-NDI-Os（III）配合物的皮秒激光闪光光解表明，在650 nm处观察到MLCT带的漂白和新带的出现。这些新带对应于Ru（III）-NDI-Os（II）态的形成。Ru（bpy）与二甲酰亚胺、Os（III）发生了分步光诱导电子转移。(3)我们发现，电喷雾电离质谱是一个强大的工具，表征和纯度检查的四核钌配合物。少

项目成果

Masa-aki Haga: ""Photoexcited states of dinuclear Ru complexes bridged by proton-dissociable benzimidazole derivates"" Coord.Chem.Rev.132. 99-104 (1994)

Masa-aki Haga：““由质子可解离的苯并咪唑衍生物桥接的双核 Ru 配合物的光激发态””Coord.Chem.Rev.132。

Masa-aki Haga: "Photoexcited states of dinuclear Ru complexes bridged by proton-dissociable benzimidazole derivatives" Coord.Chem.Rev.132. 99-104 (1994)

Masa-aki Haga：“由质子可解离的苯并咪唑衍生物桥接的双核 Ru 配合物的光激发态”Coord.Chem.Rev.132。

芳賀正明: "スイッチング機能を有する金属錯体" 化学工業. 46. 671-679 (1995)

Masaaki Haga：“具有转换功能的金属配合物” Kagaku Kogyo 46. 671-679 (1995)。

Masa-aki Haga: "Synthesis,electrochemistry and photoexcited-state properties of dinuclear ruthenium complexes bridged by 2,6'-bis(2-pvridvl)-2,2':6.2"-thiazolo[4.5-d]-benzothiazole" Inorg.Chim.Acta. 226. 17-24 (1994)

Masa-aki Haga：“2,6-双(2-pvridvl)-2,2:6.2”-噻唑并[4.5-d]-苯并噻唑桥联的双核钌配合物的合成、电化学和光激发态性质”Inorg

Masa-aki Haga: "Synthesis,electrochemistry and photoexcited-state properties of dinuclear ruthenium complexes bridged by 2,6-bis 2-pyridyl)-2,2′:6,2′-thiazolo[4,5-d]-benzothiazole." Inorg.Chim.Acta. 226. 17-24 (1994)

Masa-aki Haga：“2,6-双(2-吡啶基)-2,2′:6,2′-噻唑并[4,5-d]-苯并噻唑桥联的双核钌配合物的合成、电化学和光激发态性质” Inorg.Chim.Acta. 226. 17-24 (1994)