Gold(I)has been used as an interlocking center to design five phenyl-bipyridine based complexes[LAu(L1)]and[RAu(L2)]where L1=5-(4-ethynylphenyl)-2,2’-bipyridine and L2=5-(4-(diphenylphosphino)phenyl)-2,2’-bipyridine...Gold(I)has been used as an interlocking center to design five phenyl-bipyridine based complexes[LAu(L1)]and[RAu(L2)]where L1=5-(4-ethynylphenyl)-2,2’-bipyridine and L2=5-(4-(diphenylphosphino)phenyl)-2,2’-bipyridine(L=P(C_(6)H_(11))_(3),1;C_(6)H_(3)(CH_(3))_(2)NC,2;R=Ph_(2)OHCC_(2),3;PhC_(2),4;C_(6)F_(5),5).The obtained compounds have been characterized by polynuclear NMR spectroscopy and X-ray crystallography.Investigation of their UV-Vis absorption and emission characteristics has been supported by density functional theory(DFT)calculations that rationalize the tunable electronic properties of these compounds.Complexation of the metal cations and the corresponding optical responses of[LAu(L1)],in particular for Cd(II)and Pb(II),indicate the important role of gold(I)ions in modulating the luminescence characteristics of these species upon binding the analyte cations.展开更多
Phosphine ligands,containing chromophore substituents-π-spacer-NPh_(2)(π-spacer=biphenyl,L1;naphthalene-ethynylphenyl,L2;and ethynyl-(phenylethynyl)anthracene,L3),were used to generate the corresponding gold(I)alkyn...Phosphine ligands,containing chromophore substituents-π-spacer-NPh_(2)(π-spacer=biphenyl,L1;naphthalene-ethynylphenyl,L2;and ethynyl-(phenylethynyl)anthracene,L3),were used to generate the corresponding gold(I)alkynyl complexes Au1-Au3(alkynyl=ethynylphenyl-2,2’-bipyridine,epbpy).These compounds demonstrate intense fluorescence,which originates from the bipolar donor-π-acceptor systems of coordinated phosphines with negligible contribution from the epbpy fragment.Due to the charge transfer characteristic of the excited state,Au1-Au3 reveal significant emission solvatochromism(particularly discernible for Au2,428 nm in cyclohexane→580 nm in acetonitrile).The bipyridine moiety of Au1-Au3 was utilized for binding these metalloligands to the{Eu(tta)3}red emitter(tta=3-thenoyltrifluoroacetonate)to give a family of novel dyads Au1Eu-Au3Eu.Incomplete energy transfer from L1-L3 to lanthanide ions,which are primarily sensitized by diketonate ligands,leads to dual luminescence.Analogous to the parent complexes Au1-Au3,the fluorescence component of the dyads is highly sensitive to the solvent polarity that provides great opportunities for color tuning,including white light generation.展开更多
基金support from the Russian Science Foundation,grant 16-13-10064.
文摘Gold(I)has been used as an interlocking center to design five phenyl-bipyridine based complexes[LAu(L1)]and[RAu(L2)]where L1=5-(4-ethynylphenyl)-2,2’-bipyridine and L2=5-(4-(diphenylphosphino)phenyl)-2,2’-bipyridine(L=P(C_(6)H_(11))_(3),1;C_(6)H_(3)(CH_(3))_(2)NC,2;R=Ph_(2)OHCC_(2),3;PhC_(2),4;C_(6)F_(5),5).The obtained compounds have been characterized by polynuclear NMR spectroscopy and X-ray crystallography.Investigation of their UV-Vis absorption and emission characteristics has been supported by density functional theory(DFT)calculations that rationalize the tunable electronic properties of these compounds.Complexation of the metal cations and the corresponding optical responses of[LAu(L1)],in particular for Cd(II)and Pb(II),indicate the important role of gold(I)ions in modulating the luminescence characteristics of these species upon binding the analyte cations.
基金support from the Academy of Finland(grant 317903,I.O.K.)the Russian Science Foundation(grant 16-13-10064,photophysical and computational investigations,E.V.G.,V.V.S.,and S.O.S.).
文摘Phosphine ligands,containing chromophore substituents-π-spacer-NPh_(2)(π-spacer=biphenyl,L1;naphthalene-ethynylphenyl,L2;and ethynyl-(phenylethynyl)anthracene,L3),were used to generate the corresponding gold(I)alkynyl complexes Au1-Au3(alkynyl=ethynylphenyl-2,2’-bipyridine,epbpy).These compounds demonstrate intense fluorescence,which originates from the bipolar donor-π-acceptor systems of coordinated phosphines with negligible contribution from the epbpy fragment.Due to the charge transfer characteristic of the excited state,Au1-Au3 reveal significant emission solvatochromism(particularly discernible for Au2,428 nm in cyclohexane→580 nm in acetonitrile).The bipyridine moiety of Au1-Au3 was utilized for binding these metalloligands to the{Eu(tta)3}red emitter(tta=3-thenoyltrifluoroacetonate)to give a family of novel dyads Au1Eu-Au3Eu.Incomplete energy transfer from L1-L3 to lanthanide ions,which are primarily sensitized by diketonate ligands,leads to dual luminescence.Analogous to the parent complexes Au1-Au3,the fluorescence component of the dyads is highly sensitive to the solvent polarity that provides great opportunities for color tuning,including white light generation.
