Coinage metal_((I))complexes exhibiting thermally activated delayed fluorescence(TADF)have attracted worldwide attention as emitters for OLEDs.Reducing the emission lifetime and improving the quantum efficiency of suc...Coinage metal_((I))complexes exhibiting thermally activated delayed fluorescence(TADF)have attracted worldwide attention as emitters for OLEDs.Reducing the emission lifetime and improving the quantum efficiency of such emitters is a current challenge in this hot field.To address this issue(challenge),a symmetry-based design strategy has been applied herein to obtain pseudo-symmetric complexes[M_(2)(tdpb)(NHC)_(2)]^(2+)(M=Cu,Ag,Au)scaffolded by 1,2,4,5-tetrakis(diphenylphosphino)benzene(tdpb)and N-heterocyclic carbene(NHC)ligands.In the solid state at ambient temperature,the synthesized compounds exhibit cyan to yellow TADF of the metal-to-ligand charge transfer type with excellent quantum yields(58-89%)and short decay times(2.5-15μs).It is shown that the symmetry-based design strategy leads to a significant increase in the radiative rate constants for the“dimers”[M_(2)(tdpb)(NHC)_(2)]^(2+)compared to the“monomers”[M(dppb)(NHC)]^(+)based on 1,2-bis(diphenylphosphino)benzene(dppb).The practical potential of the developed TADF emitters was also demonstrated through their application as innovative thermo-and vapor-chromic emission inks for advanced anti-counterfeiting labels.展开更多
A series of 1D coordination polymers(CPs),[MnX_(2)(L)]_(n)(X=Cl,Br,I),made of MnX_(2)units bridged by 1,7-[Ph_(2)P(O)]_(2)-meta-carborane ligands(L)through the O-Mn-O linkages,have been designed.At ambient temperature...A series of 1D coordination polymers(CPs),[MnX_(2)(L)]_(n)(X=Cl,Br,I),made of MnX_(2)units bridged by 1,7-[Ph_(2)P(O)]_(2)-meta-carborane ligands(L)through the O-Mn-O linkages,have been designed.At ambient temperature,these CPs manifest green phosphorescence with quantum yields of up to 60%,which is the highest value for Mn(II)CPs.CP[MnI_(2)(L)]_(n)and its structurally different solvate[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)also exhibit bright triboluminescence.Thermochromic luminescence of the designed CPs appears as reversible shifting of their emission color,when the temperature varies from 350 to 77 K and back.Moreover,[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)reversibly changes its emission properties during desolvation-solvation processes thus featuring solvatochromic luminescence.According to photophysical and EPR data,the observed phosphorescence originates from the ligand-sensitized^(4)T_(1)→^(6)A_(1)transition in Mn^(2+)ions.Enhanced robustness of the title CPs is demonstrated by retaining their emission properties after prolonged heating at 210°C.展开更多
A family of robust metal complexes of[Mn(L)X_(2)]and(LH)_(2)[MnX_(4)]type(X=Cl,Br,I)have been synthesized based on xanthene-derived bisphosphine dioxides(L=XantphosO_(2)or t-Bu-XantphosO_(2)).At ambient temperature,th...A family of robust metal complexes of[Mn(L)X_(2)]and(LH)_(2)[MnX_(4)]type(X=Cl,Br,I)have been synthesized based on xanthene-derived bisphosphine dioxides(L=XantphosO_(2)or t-Bu-XantphosO_(2)).At ambient temperature,the designed compounds exhibit strong green to yellow phosphorescence with quantum yields as high as 90%.Remarkably,complex[Mn(XantphosO_(2))Br_(2)]reveals polymorphic luminescence,which is a rare phenomenon for Mn compounds.Two polymorphs of this compound,crystallizing in P1 and P2_(1)/n space groups,display green and yellow luminescence,respectively,with the emission quantum yield being 33 and 50%.Moreover,the“yellow”polymorph features bright triboluminescence upon grinding its crystals.An in-depth photophysical study evidences that the observed phosphorescence is due to the ligand-sensitized^(4)T_(1)→^(6)A_(1)transitions in Mn^(2+)ions.展开更多
基金supported by Russian Science Foundation(Project 19-73-20196)the Russian Science Foundation(Project No.22-13-00077)for financial support of the computational part of this work and the Supercomputer Centre of Novosibirsk State University for the computational resources.
文摘Coinage metal_((I))complexes exhibiting thermally activated delayed fluorescence(TADF)have attracted worldwide attention as emitters for OLEDs.Reducing the emission lifetime and improving the quantum efficiency of such emitters is a current challenge in this hot field.To address this issue(challenge),a symmetry-based design strategy has been applied herein to obtain pseudo-symmetric complexes[M_(2)(tdpb)(NHC)_(2)]^(2+)(M=Cu,Ag,Au)scaffolded by 1,2,4,5-tetrakis(diphenylphosphino)benzene(tdpb)and N-heterocyclic carbene(NHC)ligands.In the solid state at ambient temperature,the synthesized compounds exhibit cyan to yellow TADF of the metal-to-ligand charge transfer type with excellent quantum yields(58-89%)and short decay times(2.5-15μs).It is shown that the symmetry-based design strategy leads to a significant increase in the radiative rate constants for the“dimers”[M_(2)(tdpb)(NHC)_(2)]^(2+)compared to the“monomers”[M(dppb)(NHC)]^(+)based on 1,2-bis(diphenylphosphino)benzene(dppb).The practical potential of the developed TADF emitters was also demonstrated through their application as innovative thermo-and vapor-chromic emission inks for advanced anti-counterfeiting labels.
基金Russian Foundation for Basic Research(Project No.18-03-00300)。
文摘A series of 1D coordination polymers(CPs),[MnX_(2)(L)]_(n)(X=Cl,Br,I),made of MnX_(2)units bridged by 1,7-[Ph_(2)P(O)]_(2)-meta-carborane ligands(L)through the O-Mn-O linkages,have been designed.At ambient temperature,these CPs manifest green phosphorescence with quantum yields of up to 60%,which is the highest value for Mn(II)CPs.CP[MnI_(2)(L)]_(n)and its structurally different solvate[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)also exhibit bright triboluminescence.Thermochromic luminescence of the designed CPs appears as reversible shifting of their emission color,when the temperature varies from 350 to 77 K and back.Moreover,[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)reversibly changes its emission properties during desolvation-solvation processes thus featuring solvatochromic luminescence.According to photophysical and EPR data,the observed phosphorescence originates from the ligand-sensitized^(4)T_(1)→^(6)A_(1)transition in Mn^(2+)ions.Enhanced robustness of the title CPs is demonstrated by retaining their emission properties after prolonged heating at 210°C.
文摘A family of robust metal complexes of[Mn(L)X_(2)]and(LH)_(2)[MnX_(4)]type(X=Cl,Br,I)have been synthesized based on xanthene-derived bisphosphine dioxides(L=XantphosO_(2)or t-Bu-XantphosO_(2)).At ambient temperature,the designed compounds exhibit strong green to yellow phosphorescence with quantum yields as high as 90%.Remarkably,complex[Mn(XantphosO_(2))Br_(2)]reveals polymorphic luminescence,which is a rare phenomenon for Mn compounds.Two polymorphs of this compound,crystallizing in P1 and P2_(1)/n space groups,display green and yellow luminescence,respectively,with the emission quantum yield being 33 and 50%.Moreover,the“yellow”polymorph features bright triboluminescence upon grinding its crystals.An in-depth photophysical study evidences that the observed phosphorescence is due to the ligand-sensitized^(4)T_(1)→^(6)A_(1)transitions in Mn^(2+)ions.
