1988 Fiscal Year Final Research Report Summary
Synthesis and Photoracemization of Ruthenium Complexes with Six-membered Chelate Rings
| Project/Area Number |
61470048
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
無機・錯塩・放射化学
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| Research Institution | Rikkyo University |
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Principal Investigator |
MIZUMACHI Kunihiko Rikkyo University Professor, 理学部, 教授 (00062513)
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| Co-Investigator(Kenkyū-buntansha) |
TACHIYASHIKI Satoru Kagawa Nutrition College Assistant, 助手 (00076192)
ISHIMORI Tatsujiro Rikkyo University Professor, 理学部, 教授 (40062492)
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| Project Period (FY) |
1986 – 1988
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| Keywords | ruthenium complex / dipyridylamine complex / dipyridylketone complex / dipyridylmethane complex / optical resolution / ジピリジルメタン錯体 |
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| Research Abstract |
1.Synthesis of complexes
The 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 resolution
The 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. Photoracemization
The 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 project
Since 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.
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