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

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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.