Although many racemic M4L6cages have been synthesized,little attention has been paid to the resolution of M4L6cages because resolution of these cages is very difficult.To explore the use of optically pure M4L6cages in...Although many racemic M4L6cages have been synthesized,little attention has been paid to the resolution of M4L6cages because resolution of these cages is very difficult.To explore the use of optically pure M4L6cages in chiral applications,it is important to obtain a single enantiomer.In this work,the anionicΛΛΛΛ-Zr_(4)L_(6)andΛΛΛΛ-Zr_(4)L_(6)(L=embonate)cages have been completely separated by introducing chiral organic ligands R/S-BINAP and 1S,2S/1R,2R-DPEN,respectively,and the active vertex of homochiral Zr_(4)L_(6)cage trapsπ-conjugated coordination silver cations(such as[Ag_(2)(DPPM)_(2)]^(2+),chiral[Ag_(2)(PPh_(3))_(2)(DPEN)]^(2+)and[Ag(PPh_(3))(DPEN)]^(+)),obtaining two pair of pure enantiomers(PTC-375(Λ/Λ)and PTC-376(Λ/Λ)).Interestingly,the chiral resolution and surface modification of such zirconium cage endow it with homochirality and significant circularly polarized luminescence(CPL)response,and PTC-376 enantiomers show a CPL output with glumvalues up to~1.4×10^(-2).This work not only provides a new resolution strategy for metal-organic cages,but also expands their chiral application especially in CPL field.展开更多
Chiral metal-organic frameworks(MOF)composite materials hold great potential for circularly polarized luminescence(CPL)applications,but achieving circularly polarized afterglow remains significant challenging.Herein w...Chiral metal-organic frameworks(MOF)composite materials hold great potential for circularly polarized luminescence(CPL)applications,but achieving circularly polarized afterglow remains significant challenging.Herein we present a gel transformation fabrication method to synthesize carbon nanodots(CND)incorporated chiral MOF composite films with circularly polarized afterglow.A chiral amino acid based MOF gel was prepared,combined with pre-synthesized afterglow CND and coated onto an activated quartz substrate.Annealing and drying yielded the CND incorporated chiral MOF composite film(denoted as chirMOF-CND film).Due to the strong chiral transfer and synergistic interaction with gapless connection between the components of chiral MOF film and the afterglow luminophores of CND,the chiral composite film achieves high-performance circularly polarized afterglow.Additionally,the afterglow duration can be modulated by varying the CND concentration.This gel transformation strategy utilizes the unique attributes of chiral MOF and the persistent luminescence of CND for fabricating chiral composite monoliths with seamless integration,advancing next-generation optical devices and sensors applications.展开更多
The crystallization of chiral molecules is of great significance to understand the origin and evolution of hierarchical chirality and reveal the relationships between structural chirality and circularly polarized lumi...The crystallization of chiral molecules is of great significance to understand the origin and evolution of hierarchical chirality and reveal the relationships between structural chirality and circularly polarized luminescence(CPL)activity.Here,we report two pairs of chiral metal–organic frameworks(MOFs)(DCF-17/LCF-17,DCF-18/LCF-18)by utilizing tetradentate ligands tetra(3-imidazoylphenyl)ethylene(TIPE)and 4,4'-[4',5'-bis[4-(4-pyridinyl)phenyl][1,1':2',1”-terphenyl]-4,4”-diyl]bis[pyridine](TPPP)as linkers.It can be observed that the spontaneous resolution of the achiral ligands is converted into the induced resolution,and the ligands form the absolute configuration by using enantiopure camphoric acid(cam)as chiral induced reagent(CIR).As a result,the racemate MOFs can be driven to generate absolute homochiral crystallization.Another two achiral MOFs[Cd(D-cam)(TPPP)_(0.5)](AF-1,AF=achiral framework)and[Cd(L-cam)(TPPP)_(0.5)](AF-2)were prepared.The position disorder of D/L-cam skeleton causes the generation of nonchiralization,further leading to disappearance of symmetry breaking of TPPP.For the perspective of structure,this is the first report which reveals the chiral transfer and nonchiralization between chiral induced agents and tetradentate ligands.Besides,DCF-17 and LCF-17 show CPL with luminescence dissymmetry factor(glum)of–1.0×10^(-2)and+9.2×10^(–3),respectively.This work provides the useful evidences to reveal the induced chiral crystallization and the construction of CPL-active crystalline materials.展开更多
Tin oxides(SnO_(2))have been widely utilized in electronics,nanolithography,and catalysis.As the atomically precise models of SnO_(2),tin-oxo clusters(TOCs)not only provide opportunities for mechanism studies,but they...Tin oxides(SnO_(2))have been widely utilized in electronics,nanolithography,and catalysis.As the atomically precise models of SnO_(2),tin-oxo clusters(TOCs)not only provide opportunities for mechanism studies,but they also extend potential applications through structural modulation.However,to date,most of the reported TOCs belong to alkyl organotin complexes,which are usually toxic to the human body and the active sites are difficult to expose for catalysis.展开更多
基金supported by the National Natural Science Foundation of China(Nos.92261108 and 2022YFA1503303)the STS Project of Fujian-CAS(No.2023T3054)。
文摘Although many racemic M4L6cages have been synthesized,little attention has been paid to the resolution of M4L6cages because resolution of these cages is very difficult.To explore the use of optically pure M4L6cages in chiral applications,it is important to obtain a single enantiomer.In this work,the anionicΛΛΛΛ-Zr_(4)L_(6)andΛΛΛΛ-Zr_(4)L_(6)(L=embonate)cages have been completely separated by introducing chiral organic ligands R/S-BINAP and 1S,2S/1R,2R-DPEN,respectively,and the active vertex of homochiral Zr_(4)L_(6)cage trapsπ-conjugated coordination silver cations(such as[Ag_(2)(DPPM)_(2)]^(2+),chiral[Ag_(2)(PPh_(3))_(2)(DPEN)]^(2+)and[Ag(PPh_(3))(DPEN)]^(+)),obtaining two pair of pure enantiomers(PTC-375(Λ/Λ)and PTC-376(Λ/Λ)).Interestingly,the chiral resolution and surface modification of such zirconium cage endow it with homochirality and significant circularly polarized luminescence(CPL)response,and PTC-376 enantiomers show a CPL output with glumvalues up to~1.4×10^(-2).This work not only provides a new resolution strategy for metal-organic cages,but also expands their chiral application especially in CPL field.
基金granted by National Key R&D Program of China(No.2022YFA1503300)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.Y2022081)+1 种基金Natural Science Foundation of Fujian Province(No.2022J06031)the STS Project of Fujian-CAS(Nos.2023T3003 and 2023T3052).
文摘Chiral metal-organic frameworks(MOF)composite materials hold great potential for circularly polarized luminescence(CPL)applications,but achieving circularly polarized afterglow remains significant challenging.Herein we present a gel transformation fabrication method to synthesize carbon nanodots(CND)incorporated chiral MOF composite films with circularly polarized afterglow.A chiral amino acid based MOF gel was prepared,combined with pre-synthesized afterglow CND and coated onto an activated quartz substrate.Annealing and drying yielded the CND incorporated chiral MOF composite film(denoted as chirMOF-CND film).Due to the strong chiral transfer and synergistic interaction with gapless connection between the components of chiral MOF film and the afterglow luminophores of CND,the chiral composite film achieves high-performance circularly polarized afterglow.Additionally,the afterglow duration can be modulated by varying the CND concentration.This gel transformation strategy utilizes the unique attributes of chiral MOF and the persistent luminescence of CND for fabricating chiral composite monoliths with seamless integration,advancing next-generation optical devices and sensors applications.
基金supported by the National Natural Science Foundation of China(22171123,22102068)the Natural Science Foundation for Excellent Young Scholars of Henan Province(232300421083,212300410061)+3 种基金the Program for Innovative Research Team from the University of Henan Province(24IRTSTHN005)the Science and Technology R&D Program of the Joint Funds of Henan Province(225200810082)the Open Foundation of State Key Laboratory of Structural Chemistry(20230021)Scientific and Technological Support Project of Guizhou Province(Qian Ke He Zhi Cheng[2023]Yi Ban 262).
文摘The crystallization of chiral molecules is of great significance to understand the origin and evolution of hierarchical chirality and reveal the relationships between structural chirality and circularly polarized luminescence(CPL)activity.Here,we report two pairs of chiral metal–organic frameworks(MOFs)(DCF-17/LCF-17,DCF-18/LCF-18)by utilizing tetradentate ligands tetra(3-imidazoylphenyl)ethylene(TIPE)and 4,4'-[4',5'-bis[4-(4-pyridinyl)phenyl][1,1':2',1”-terphenyl]-4,4”-diyl]bis[pyridine](TPPP)as linkers.It can be observed that the spontaneous resolution of the achiral ligands is converted into the induced resolution,and the ligands form the absolute configuration by using enantiopure camphoric acid(cam)as chiral induced reagent(CIR).As a result,the racemate MOFs can be driven to generate absolute homochiral crystallization.Another two achiral MOFs[Cd(D-cam)(TPPP)_(0.5)](AF-1,AF=achiral framework)and[Cd(L-cam)(TPPP)_(0.5)](AF-2)were prepared.The position disorder of D/L-cam skeleton causes the generation of nonchiralization,further leading to disappearance of symmetry breaking of TPPP.For the perspective of structure,this is the first report which reveals the chiral transfer and nonchiralization between chiral induced agents and tetradentate ligands.Besides,DCF-17 and LCF-17 show CPL with luminescence dissymmetry factor(glum)of–1.0×10^(-2)and+9.2×10^(–3),respectively.This work provides the useful evidences to reveal the induced chiral crystallization and the construction of CPL-active crystalline materials.
基金supported by the National Natural Science Foundation of China(nos.91961108,21922111,and 21973094)the National Key Research and Development Program of China(no.2017YFA0206801)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(no.XDB20000000)the Natural Science Foundation of Fujian Province(no.2019J01131).
文摘Tin oxides(SnO_(2))have been widely utilized in electronics,nanolithography,and catalysis.As the atomically precise models of SnO_(2),tin-oxo clusters(TOCs)not only provide opportunities for mechanism studies,but they also extend potential applications through structural modulation.However,to date,most of the reported TOCs belong to alkyl organotin complexes,which are usually toxic to the human body and the active sites are difficult to expose for catalysis.
