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 clusters(cMOCs)are characterized by diverse chiral origins,tunable luminescence,and multifunctionality.Among them,chiral aluminum oxo clusters(AlOCs)exhibit unique advantages in terms of resource ...Chiral metal-organic clusters(cMOCs)are characterized by diverse chiral origins,tunable luminescence,and multifunctionality.Among them,chiral aluminum oxo clusters(AlOCs)exhibit unique advantages in terms of resource sustainability and environmental friendliness compared to other cluster materials.Nevertheless,the simultaneous achievement of precise enantiomeric control and optical response within AlOCs remains a critical challenge to be addressed in the field.Herein,we achieve precise control over the transition from chirality to circularly polarized luminescence properties in AlOCs by leveraging their highly flexible and modifiable coordination surfaces through a stepwise ligand functionalization strategy.We employed the Al2cluster as a platform with programmable surface coordination sites and introduced classical chiral L/D-valine molecules.We successfully constructed four pairs of alcohol-coordinated pure chiral enantiomers(AlOC-189-L/D-MeOH,EtOH,PrOH,and PDO).Absolute helical structures can be identified in the supramolecular architectures of clusters,achieving unambiguous chirality transfer from chiral ligands to chiral clusters and further to absolute helical superstructures.Hierarchical ligand modification,endowed with a top-down design paradigm,offers a rational and feasible route to cluster functionalization.Based on the excellent replaceability of the Al_(2)cluster's surface coordination sites,we achieved chiral-luminescent bifunctional coupling by partially substituting the chiral ligands withπ-conjugated naphthyl-based luminophores(HNA/HNN),yielding two new classes of enantiomers(AlOC-190-L/D-HNA and AlOC-190-L/D-HNN)exhibiting bright yellow-green photoluminescence(PL).DFT calculations reveal that this is attributed to a ligand-to-ligand charge transfer(LLCT)luminescence mechanism.Notably,AlOC-190-L/D-HNN exhibited promising circularly polarized luminescence(CPL)activity via the synergy between chiral induction from L/D-valine ligands and intermolecular charge transfer of the HNN ligands.This work not only highlights the highly designable coordination chemistry of AlOC-enabling on-demand integration of specific functionalities through modular ligand substitution-but also establishes a novel"ligand editing"paradigm for developing multifunctional chiral optical materials.展开更多
Supracluster assembly offers a unique opportunity for the isolation of customized materials using functional cluster precursors.Herein,for the first time,we demonstrate supracluster assembly based on an Al_(4)^(4−)pre...Supracluster assembly offers a unique opportunity for the isolation of customized materials using functional cluster precursors.Herein,for the first time,we demonstrate supracluster assembly based on an Al_(4)^(4−)precursor through both non-covalent interactions and coordination bonds.By reacting readily available,ultrastable,and soluble Al_(4)^(4−)as an anionic precursor with a metal center and neutral chelated chromophores,we successfully synthesized an extensive library of supracluster assembled crystalline solids,ranging from ion-pair structures,surface-modified clusters,and chains,to layered compounds.The advantage of this method is that it achieves stepwise performance regulation and enhancement using given functional precursors.These materials from supracluster assembly possess a broad range of tunable photophysical properties,including photoluminescence and third-order nonlinear optical(NLO)properties.Such extraordinary supracluster assembly will be widely applicable for creating a new generation of rationally organized solid materials with tailorable and customized properties.展开更多
Benefiting from the strong inherent π-conjugation properties,the integration of Ti_(4)L_(6)(L=embonate)cages and various N,N-chelated transition-metal cations into tightly packed structures accurately leads to high-p...Benefiting from the strong inherent π-conjugation properties,the integration of Ti_(4)L_(6)(L=embonate)cages and various N,N-chelated transition-metal cations into tightly packed structures accurately leads to high-performance materials with adjustable nonlinear optical(NLO)effects.These cage-based ionic pairs possess different supramolecular packing structures,including a π⋯π stacked porous framework where the Ti_(4)L_(6) cages are tactically located at the channels.Interestingly,by introducing the large π-conjugated 1,10-phenanthroline type ligands and adjusting the aromatic ring electron cloud density,we have effectively regulated their third-order NLO properties,realizing nonlinear absorption responses from reverse saturated absorption(RSA)to saturated absorption(SA).This work not only presents an extraordinary coordination cage-based assembly,but also provides new insights into the function of cage materials.展开更多
Herein the chiral resolution of racemic Zr_(4)L_(6)tetrahedral cages has been realized using luminescent enantiopure coordination cations.Accordingly,anionicΔΔΔΔ-Zr_(4)L_(6)andΛΛΛΛ-Zr_(4)L_(6)cages(L=embonate)...Herein the chiral resolution of racemic Zr_(4)L_(6)tetrahedral cages has been realized using luminescent enantiopure coordination cations.Accordingly,anionicΔΔΔΔ-Zr_(4)L_(6)andΛΛΛΛ-Zr_(4)L_(6)cages(L=embonate)were completely resolved using enantiopure[Ag(R-BINAP)2]^(+)and[Ag(S-BINAP)2]^(+)cations,respectively,and a pair of pure enantiomers(PTC-374(R,Δ)and PTC-374(S,Λ);PTC=polynuclear titanium cage)were easily prepared and structurally well-characterized,featuring an uncommon cage-supported supramolecular framework with zeolitic SOD topology.The stepwise transfer of homochirality can be clearly observed in the unusual resolution process.Moreover,the perfect combination of two functional components endows such co-assembled materials with synergistic circular dichroism performance,enhanced fluorescence and circularly polarized luminescence response.展开更多
Herein,we demonstrate a very useful strategy to construct cage-based metal-organic frameworks(MOFs)with third-order nonlinear-optical properties.More specifically,by employing the Zr_(4)L_(6)(L=embonate)cages to assem...Herein,we demonstrate a very useful strategy to construct cage-based metal-organic frameworks(MOFs)with third-order nonlinear-optical properties.More specifically,by employing the Zr_(4)L_(6)(L=embonate)cages to assembly with N-contained ligands and Mn^(2+)/Zn^(2+) ions,four Zr_(4)L_(6)-cage-based MOFs have been synthesized and structurally characterized.Among them,a 3D framework with strong aromatic π−πstacking force exhibits a good optical limiting effect.展开更多
Post-assembly modification strategy is used as an effective approach to improve the functional applications of metal-organic cages. The active vertex of the racemic tetrahedral Ti4L6(L = embonate) cages traps four chi...Post-assembly modification strategy is used as an effective approach to improve the functional applications of metal-organic cages. The active vertex of the racemic tetrahedral Ti4L6(L = embonate) cages traps four chiral diamine chelated dinuclear silver ions, obtaining homochiral cages which exhibit helical perovskite stacks. Such a surface modification engineering enables the structural precise cages presenting homochirality and circularly polarized luminescence(CPL) response, further achieving enantioselective recognition toward chiral Camphorquinone molecules and displaying enhanced temperature-dependent effects of CPL output.展开更多
To realize the application of the floating offshore wind turbine(FOWT)from deep to relatively shallow waters,a new concept of multi-column floating wind turbine platform with low center of gravity(CG)is designed and v...To realize the application of the floating offshore wind turbine(FOWT)from deep to relatively shallow waters,a new concept of multi-column floating wind turbine platform with low center of gravity(CG)is designed and validated.The multi-column low CG platform is designed to support a 6MW wind turbine class and operated at a water depth of 50m in the South China Sea.The frequency domain software WADAM and time domain software NREL-FAST are used to simulate coupled dynamic responses of the floating wind turbine system with second-order wave loads considering.The dynamic behaviors of multi-column low CG FOWT system under normal operation and parked conditions are presented.The influence of second-order wave force on the motion responses of the multi-column platform,fore-aft force and moment of the tower base and mooring force are researched respectively.The results demonstrate that the coupled dynamic responses at rated operating condition and extreme condition meet the normal operating requirements and extreme survival requirements of FOWT system in the shallow water(50m)of South China Sea.In addition,it is found that,the wave frequency response gradually replaces the second-order low frequency response as the main influencing factor of the coupled dynamic response of the FOWT system with the increasing severity of the sea states.However,in general,the magnitude of second-order low frequency response increases with the increasing severity of the design load case.Thus,in the subsequent design of the shallow water FOWT system,the second-order effects should be paid enough attention.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supported by the National Natural Science Foundation of China(22371278,92261108,92061104)the Natural Science Foundation of Fujian Province(2021J06035)+1 种基金the Fujian Provincial Department of Science and Technology(#2023T3081)the Youth Innovation Promotion Association Chinese Academy of Sciences(Y2021081).
文摘Chiral metal-organic clusters(cMOCs)are characterized by diverse chiral origins,tunable luminescence,and multifunctionality.Among them,chiral aluminum oxo clusters(AlOCs)exhibit unique advantages in terms of resource sustainability and environmental friendliness compared to other cluster materials.Nevertheless,the simultaneous achievement of precise enantiomeric control and optical response within AlOCs remains a critical challenge to be addressed in the field.Herein,we achieve precise control over the transition from chirality to circularly polarized luminescence properties in AlOCs by leveraging their highly flexible and modifiable coordination surfaces through a stepwise ligand functionalization strategy.We employed the Al2cluster as a platform with programmable surface coordination sites and introduced classical chiral L/D-valine molecules.We successfully constructed four pairs of alcohol-coordinated pure chiral enantiomers(AlOC-189-L/D-MeOH,EtOH,PrOH,and PDO).Absolute helical structures can be identified in the supramolecular architectures of clusters,achieving unambiguous chirality transfer from chiral ligands to chiral clusters and further to absolute helical superstructures.Hierarchical ligand modification,endowed with a top-down design paradigm,offers a rational and feasible route to cluster functionalization.Based on the excellent replaceability of the Al_(2)cluster's surface coordination sites,we achieved chiral-luminescent bifunctional coupling by partially substituting the chiral ligands withπ-conjugated naphthyl-based luminophores(HNA/HNN),yielding two new classes of enantiomers(AlOC-190-L/D-HNA and AlOC-190-L/D-HNN)exhibiting bright yellow-green photoluminescence(PL).DFT calculations reveal that this is attributed to a ligand-to-ligand charge transfer(LLCT)luminescence mechanism.Notably,AlOC-190-L/D-HNN exhibited promising circularly polarized luminescence(CPL)activity via the synergy between chiral induction from L/D-valine ligands and intermolecular charge transfer of the HNN ligands.This work not only highlights the highly designable coordination chemistry of AlOC-enabling on-demand integration of specific functionalities through modular ligand substitution-but also establishes a novel"ligand editing"paradigm for developing multifunctional chiral optical materials.
基金supported by the National Natural Science Foundation of China(U23A20950,22371278,and 92261108)the Science Fund for Distinguished Young Scholars of Fujian Province(2021J06035)+1 种基金the Funding of the Fujian Provincial Chemistry Discipline Alliance(50025401)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(Y2021081).
文摘Supracluster assembly offers a unique opportunity for the isolation of customized materials using functional cluster precursors.Herein,for the first time,we demonstrate supracluster assembly based on an Al_(4)^(4−)precursor through both non-covalent interactions and coordination bonds.By reacting readily available,ultrastable,and soluble Al_(4)^(4−)as an anionic precursor with a metal center and neutral chelated chromophores,we successfully synthesized an extensive library of supracluster assembled crystalline solids,ranging from ion-pair structures,surface-modified clusters,and chains,to layered compounds.The advantage of this method is that it achieves stepwise performance regulation and enhancement using given functional precursors.These materials from supracluster assembly possess a broad range of tunable photophysical properties,including photoluminescence and third-order nonlinear optical(NLO)properties.Such extraordinary supracluster assembly will be widely applicable for creating a new generation of rationally organized solid materials with tailorable and customized properties.
基金supported by the National Natural Science Foundation of China(21935010)the China National Postdoctoral Program for Innovative Talents(BX2021316)the China Postdoctoral Science Foundation(2021M703217).
文摘Benefiting from the strong inherent π-conjugation properties,the integration of Ti_(4)L_(6)(L=embonate)cages and various N,N-chelated transition-metal cations into tightly packed structures accurately leads to high-performance materials with adjustable nonlinear optical(NLO)effects.These cage-based ionic pairs possess different supramolecular packing structures,including a π⋯π stacked porous framework where the Ti_(4)L_(6) cages are tactically located at the channels.Interestingly,by introducing the large π-conjugated 1,10-phenanthroline type ligands and adjusting the aromatic ring electron cloud density,we have effectively regulated their third-order NLO properties,realizing nonlinear absorption responses from reverse saturated absorption(RSA)to saturated absorption(SA).This work not only presents an extraordinary coordination cage-based assembly,but also provides new insights into the function of cage materials.
基金supported by the National Natural Science Foundation of China(92261108 and 21935010)the STS Project of Fujian-CAS(2023T3054).
文摘Herein the chiral resolution of racemic Zr_(4)L_(6)tetrahedral cages has been realized using luminescent enantiopure coordination cations.Accordingly,anionicΔΔΔΔ-Zr_(4)L_(6)andΛΛΛΛ-Zr_(4)L_(6)cages(L=embonate)were completely resolved using enantiopure[Ag(R-BINAP)2]^(+)and[Ag(S-BINAP)2]^(+)cations,respectively,and a pair of pure enantiomers(PTC-374(R,Δ)and PTC-374(S,Λ);PTC=polynuclear titanium cage)were easily prepared and structurally well-characterized,featuring an uncommon cage-supported supramolecular framework with zeolitic SOD topology.The stepwise transfer of homochirality can be clearly observed in the unusual resolution process.Moreover,the perfect combination of two functional components endows such co-assembled materials with synergistic circular dichroism performance,enhanced fluorescence and circularly polarized luminescence response.
基金supported by the National Natural Science Foundation of China(21922111,21871050 and 21975288)the Natural Science Foundation of Fujian Province(2017J06009).
文摘Herein,we demonstrate a very useful strategy to construct cage-based metal-organic frameworks(MOFs)with third-order nonlinear-optical properties.More specifically,by employing the Zr_(4)L_(6)(L=embonate)cages to assembly with N-contained ligands and Mn^(2+)/Zn^(2+) ions,four Zr_(4)L_(6)-cage-based MOFs have been synthesized and structurally characterized.Among them,a 3D framework with strong aromatic π−πstacking force exhibits a good optical limiting effect.
基金supported by the National Natural Science Foundation of China (21935010, 92261108, 92161105)the China National Postdoctoral Program for Innovative Talents (BX2021316)the China Postdoctoral Science Foundation (2021M703217)。
文摘Post-assembly modification strategy is used as an effective approach to improve the functional applications of metal-organic cages. The active vertex of the racemic tetrahedral Ti4L6(L = embonate) cages traps four chiral diamine chelated dinuclear silver ions, obtaining homochiral cages which exhibit helical perovskite stacks. Such a surface modification engineering enables the structural precise cages presenting homochirality and circularly polarized luminescence(CPL) response, further achieving enantioselective recognition toward chiral Camphorquinone molecules and displaying enhanced temperature-dependent effects of CPL output.
基金support from the National Natural Science Foundation of China (No.51809170 and No.12102210)State Key Laboratory of Ocean Engi-neering (No.GKZD010081)Programfor International Coopera-tion of Shanghai Science and Technology (No.18160744000).
文摘To realize the application of the floating offshore wind turbine(FOWT)from deep to relatively shallow waters,a new concept of multi-column floating wind turbine platform with low center of gravity(CG)is designed and validated.The multi-column low CG platform is designed to support a 6MW wind turbine class and operated at a water depth of 50m in the South China Sea.The frequency domain software WADAM and time domain software NREL-FAST are used to simulate coupled dynamic responses of the floating wind turbine system with second-order wave loads considering.The dynamic behaviors of multi-column low CG FOWT system under normal operation and parked conditions are presented.The influence of second-order wave force on the motion responses of the multi-column platform,fore-aft force and moment of the tower base and mooring force are researched respectively.The results demonstrate that the coupled dynamic responses at rated operating condition and extreme condition meet the normal operating requirements and extreme survival requirements of FOWT system in the shallow water(50m)of South China Sea.In addition,it is found that,the wave frequency response gradually replaces the second-order low frequency response as the main influencing factor of the coupled dynamic response of the FOWT system with the increasing severity of the sea states.However,in general,the magnitude of second-order low frequency response increases with the increasing severity of the design load case.Thus,in the subsequent design of the shallow water FOWT system,the second-order effects should be paid enough attention.
