The bis(phosphine)-functionalizedβ-diketiminate ligand[HC{(CH_(3))C}_(2){(o-[P(C_(6)H_(5))_(2)]_(2)C_(6)H_(4))N}_(2)]^(−)(PNac)was used for the synthesis of luminescent closed-shell bimetallic complexes.The PNNP pock...The bis(phosphine)-functionalizedβ-diketiminate ligand[HC{(CH_(3))C}_(2){(o-[P(C_(6)H_(5))_(2)]_(2)C_(6)H_(4))N}_(2)]^(−)(PNac)was used for the synthesis of luminescent closed-shell bimetallic complexes.The PNNP pocket combin ing both soft and hard donor sites can act as an orthogonal ligand scaffold to selectively coordinate two different metal ions.Deprotonation and subsequent salt elimination with[AuCl(tht)](tht=tetrahydrothio phene)or AgI yielded the mononuclear complexes[PNacAu](1)or[PNacAg](2),respectively.The Au^(Ⅰ)ion is linearly coordinated by the two phosphines,forming a 12-membered metalla-macrocycle with an emptyß-diketiminate pocket available for complexation of hard d10 metal ions(Zn^(Ⅱ),Cd^(Ⅱ),and Hg^(Ⅱ)).According to this synthetic protocol,a series of heterobimetallic complexes were isolated.The complexa tion of the second metal ion in close spatial proximity has led to drastic changes in the photophysical pro perties.For further studies and understanding,quantum chemical calculations were performed.展开更多
基金Deutsche Forschungsgemeinschaft(DFG)for financial support through the Transregional Collaborative Research Centre CRC/TRR 88“Cooperative Effects in Homo-and Heterometallic Complexes(3MET)”(Projects C1 and C3).
文摘The bis(phosphine)-functionalizedβ-diketiminate ligand[HC{(CH_(3))C}_(2){(o-[P(C_(6)H_(5))_(2)]_(2)C_(6)H_(4))N}_(2)]^(−)(PNac)was used for the synthesis of luminescent closed-shell bimetallic complexes.The PNNP pocket combin ing both soft and hard donor sites can act as an orthogonal ligand scaffold to selectively coordinate two different metal ions.Deprotonation and subsequent salt elimination with[AuCl(tht)](tht=tetrahydrothio phene)or AgI yielded the mononuclear complexes[PNacAu](1)or[PNacAg](2),respectively.The Au^(Ⅰ)ion is linearly coordinated by the two phosphines,forming a 12-membered metalla-macrocycle with an emptyß-diketiminate pocket available for complexation of hard d10 metal ions(Zn^(Ⅱ),Cd^(Ⅱ),and Hg^(Ⅱ)).According to this synthetic protocol,a series of heterobimetallic complexes were isolated.The complexa tion of the second metal ion in close spatial proximity has led to drastic changes in the photophysical pro perties.For further studies and understanding,quantum chemical calculations were performed.
