Synthesis and Photoracemization of Ruthenium Complexes with Six-membered Chelate Rings

六元螯合钌配合物的合成及光外消旋化

• 批准号: 61470048
• 负责人: MIZUMACHI Kunihiko
• 金额: $ 3.33万
• 依托单位: Rikkyo University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61470048/
• 关键词: ruthenium complex; dipyridylamine complex; dipyridylketone complex; dipyridylmethane complex; optical resolution; ジピリジルメタン錯体; ジピリジルアミン錯体; ジピルジルメタン錯体; 円偏光二色性スペクトル; 錯体の光学分割; ジピリジルケトンールテニウム錯体; ジピリジルアミンールテニウム錯体; ジピリジルメタンールテニウム錯体; ジピリジルアミン-ルテニウム錯体

1.Synthesis of complexesThe synthesis of a series of complexes with a formula of [Ru(bpy)<@D2n@>D2(L)<@D23-n@>D2]X<@D22@>D2 has been developed {L = di-2-pyridylamine (HDPA), di-2-pyridylketone (dpk), or di-2-pyridylmethane (dpm);n = 0-2}. The following new complexes were synthesized. [Ru(bpy)<@D2n@>D2(Hdpa)<@D3-n@>D2]X<@D22@>D2 (n = 0-2, X = PF<@D26@>D2, C10<@D24@>D2, CF<@D23@>D2SO<@D23@>D), ッ[Ru(bpy)<@D22@>D2(dpk)](C10<@D24@>D2)<@D22@>D2・h<@D22@>D2O, [Ru(bpy)<@D22@>D2(dpm)](PF<@D26@>D2)<@D22@>D2・H<@D22@>D2O.The following complexes were also newly obtained. [RuC1<@D22@>D2(dpk)<@D@>D2]Cl, [Ru(dpkOH)<@d22@>d2]Cl.2. Optical resolutionThe following coplexes were resolved through SP-Sephadex cation exchange chromatography or precipitation of diastereomers. Dibenzoyltartrate was effective resolving agent. [Ru(bpy)_n(Hdpa)_<3-n>]^<2+> ( n = 0-2), [Ru(bpy)_2(dpm)]^<2+>, [Ru(bpy)_2(dipyridylemthanoe)]^<2+>.3. PhotoracemizationThe quantum yield of photoracemization were measured for act-[Ru(Hdpa)_3]^<2+> and act-[Ru(bpy)_2(Hdpa)]^<2+>. Themperature dependencyof quantum yield was quite similar to the case of [Ru(bpy)_3]^<2+>. The racemization may probably occur from the exited ^3Lf state.4. Future projectSince the synthesis and the optical resolution have been well established the next step of the present work will be the determination of the quantum yields of photoracemization, and the life-time of emission of the series of the complexes at varying temperture.

1.络合物的合成开发了一系列分子式为[Ru(bpy)<@D2n@>D2(L)<@D23-n@>D2]X<@D22@>D2的络合物{L =二-2-吡啶胺（HDPA）、二-2-吡啶酮（dpk）或二-2-吡啶基甲烷（dpm）；N = 0-2}。合成了以下新的配合物。[俄文(bpy) < @D2n@ > D2 (Hdpa) < @D3-n@ > D2) X < @D22@ > D2 (n = 0, X = PF < @D26@ > D2, C10 < @D24@ > D2, CF < @D23@ > D2SO < @D23@ > D),ッ[俄文(bpy) < @D22@ > D2 (dpk)] (C10 < @D24@ > D2) < @D22@ > D2・h < @D22@ > D2O,[俄文(bpy) < @D22@ > D2 (dpm)] (PF < @D26@ > D2) < @D22@ > D2・h < @D22@ > D2O。以下配合物也是新获得的。[RuC1 < @D22@ > D2 (dpk) < @D@ > D2] Cl,[俄文(dpkOH) < @D22@ > D2) Cl.2。光学解析通过SP-Sephadex阳离子交换色谱法或非对映体沉淀法分离出以下配合物。酒石酸二苯甲酯是有效的溶解剂。[俄文(bpy) _n”(Hdpa) _ < 3 n >] ^ < 2 + > (n = 0),[俄文(bpy) _2 (dpm)] ^ < 2 + >,[俄文(bpy) _2 (dipyridylemthanoe)] ^ < 2 + >。3。测定了act-[Ru(Hdpa)_3]^<2+>和act-[Ru(bpy)_2(Hdpa)]^<2+>的光消酰基化量子产率。量子产率的温度依赖性与[Ru(bpy)_3]^<2+>的情况非常相似。外消旋作用可能发生在^3Lf态。由于合成和光学分辨率已经很好地建立，本工作的下一步将是确定光消旋化的量子产率和一系列配合物在不同温度下的发射寿命。

项目成果

三木: Bull.Chem.Soc.Jpn.59. 3275-3276 (1986)

三木：Bull.Chem.Soc.Jpn.59 (1986)。

鎌田: Chem.Lett.159-162 (1988)

蒲田：Chem.Lett.159-162 (1988)

伊藤,水町: Bull.Chem.Soc.Jpn.

伊藤水町：Bull.Chem.Soc.Jpn。

立屋敷: Proc.xxvi.Int.Cont.Coord.Chem.B42 (1988)

立屋敷：Proc.xxvi.Int.Cont.Coord.Chem.B42 (1988)

福地: Bull.Chem.Soc.Jpn.(1989)

福地：Bull.Chem.Soc.Jpn.(1989)