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
The octahedral chalcocyanide cluster anion[Re_(6)S_(8)(CN)_(6)]^(4-)can serve as a metallolinker for the self-assembly of metal-organic frameworks(MOFs)comprising polynuclear lanthanide complexes,which have been illus...The octahedral chalcocyanide cluster anion[Re_(6)S_(8)(CN)_(6)]^(4-)can serve as a metallolinker for the self-assembly of metal-organic frameworks(MOFs)comprising polynuclear lanthanide complexes,which have been illustrated for a series of nine compounds isolated as[{Ln_(4)(μ_(3)-OH)_(4)(ina)_(4)(H_(2)O)n}{Re_(6)S_(8)(CN)_(6)}]·mH_(2)O(Ln=Pr-Er,ina=isonicotinate).Their solid-state framework structures are based on{Ln_(4)(μ_(3)-OH)_(4)}^(8+)cubane fragments interlinked by isonicotinate and rhenium cyanide clusters.The coordination environment of the lanthanide ions,the coordination numbers and even the number of bridging isonicotinate moieties changes systematically within the lanthanide row,however,the framework topology remains unchanged,confirming the structure-directing role of the rhenium cluster.Structures,magnetochemical properties,luminescence and thermal stability of the new MOFs have been thoroughly analyzed.展开更多
The first observation of luminescence from Ag(I)complexes with a square-planar geometry of the metal is reported.[Ag(Py_(3)PO)_(2)]ClO_(4)and[Ag(Py_(3)PO)_(2)]OTf-first examples of the emissive square-planar Ag(I)comp...The first observation of luminescence from Ag(I)complexes with a square-planar geometry of the metal is reported.[Ag(Py_(3)PO)_(2)]ClO_(4)and[Ag(Py_(3)PO)_(2)]OTf-first examples of the emissive square-planar Ag(I)complexes-have been synthesized by the reaction of tris(2-pyridyl)phosphine oxide(Py_(3)PO)with Ag(I)salts.Both complexes exhibit pronounced photoluminescence in the solid state at ambient temperature with nano-and microsecond lifetime components.Remarkably,the luminescence of the complexes has a reversible thermochromic behavior,changing their emission color from yellow(λ_(max)^(em)≈585 nm)at room temperature to red-orange(λ_(max)^(em)=620 nm)at 77 K.The spectroscopic and computational results reveal that the emission of the title compounds can be assigned to the 3MLCT phosphorescence with admixture of the 1MLCT fluorescence.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The octahedral chalcocyanide cluster anion[Re_(6)S_(8)(CN)_(6)]^(4-)can serve as a metallolinker for the self-assembly of metal-organic frameworks(MOFs)comprising polynuclear lanthanide complexes,which have been illustrated for a series of nine compounds isolated as[{Ln_(4)(μ_(3)-OH)_(4)(ina)_(4)(H_(2)O)n}{Re_(6)S_(8)(CN)_(6)}]·mH_(2)O(Ln=Pr-Er,ina=isonicotinate).Their solid-state framework structures are based on{Ln_(4)(μ_(3)-OH)_(4)}^(8+)cubane fragments interlinked by isonicotinate and rhenium cyanide clusters.The coordination environment of the lanthanide ions,the coordination numbers and even the number of bridging isonicotinate moieties changes systematically within the lanthanide row,however,the framework topology remains unchanged,confirming the structure-directing role of the rhenium cluster.Structures,magnetochemical properties,luminescence and thermal stability of the new MOFs have been thoroughly analyzed.
基金supported by the Russian Science Foundation(Project 18-73-10086).The part of photophysical measurements was carried out in the Centre for Optical and Laser Materials Research of Saint Petersburg State University Research Park.The authors are grateful to the Multi-Access Chemical Service Center SB RAS for single crystal XRD analysis.
文摘The first observation of luminescence from Ag(I)complexes with a square-planar geometry of the metal is reported.[Ag(Py_(3)PO)_(2)]ClO_(4)and[Ag(Py_(3)PO)_(2)]OTf-first examples of the emissive square-planar Ag(I)complexes-have been synthesized by the reaction of tris(2-pyridyl)phosphine oxide(Py_(3)PO)with Ag(I)salts.Both complexes exhibit pronounced photoluminescence in the solid state at ambient temperature with nano-and microsecond lifetime components.Remarkably,the luminescence of the complexes has a reversible thermochromic behavior,changing their emission color from yellow(λ_(max)^(em)≈585 nm)at room temperature to red-orange(λ_(max)^(em)=620 nm)at 77 K.The spectroscopic and computational results reveal that the emission of the title compounds can be assigned to the 3MLCT phosphorescence with admixture of the 1MLCT fluorescence.
