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
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(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.
