Versatile stimuli-responsive circularly polarized luminescent(CPL)materials have potential applications in information storage,security encryption,and intelligent displays.In this study,the Z/E isomerization of ultrav...Versatile stimuli-responsive circularly polarized luminescent(CPL)materials have potential applications in information storage,security encryption,and intelligent displays.In this study,the Z/E isomerization of ultraviolet(UV)-photosensitive achiralα-cyanostilbene derivative was used as an achiral dichroic dye(Switch)to drive the controllable CPL-active response in cholesteric liquid crystals(CLCs).Under irradiation by 365 nm UV light,the resulting CLCs-Z-Switch underwent a Z-to-E configuration isomerization as CLCs-E-Switch,accompanied by a decrease in its dichroic order parameter(SFvalue)from 0.15to 0.07.Although the quantum yield(QY)of CLCs-E-Switch increased from 8.1%(CLCs-Z-Switch)to 16.8%,the corresponding glumvalues of CPL emission decreased from+0.55/-0.57 to+0.37/-0.39 due to a decrease in the order of helical arrangement of E-Switch in E7 media.This study enables photosensitive CLCs-Switch to be applied for optical information storage devices.展开更多
Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilita...Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31%at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.展开更多
Recently,organic-inorganic hybrid metal halides(HMHs)have attracted extensive attention as promis-ing multifunctional materials by virtue of their structural diversity and tunable photophysical properties.However,it r...Recently,organic-inorganic hybrid metal halides(HMHs)have attracted extensive attention as promis-ing multifunctional materials by virtue of their structural diversity and tunable photophysical properties.However,it remains a challenge to design HMHs with specific functions on demand.Herein,by introduc-ing R/S-methylbenzylamine(R/S-MBA)and doping Sb^(3+),we have achieved both second harmonic gen-eration(SHG)and circularly polarized luminescence(CPL)properties in lead-free indium halides.The introduction of chiral organic cations can break the symmetry and induce the indium halides to crys-tallize in the chiral space group.The Sb^(3+)with ns2 electronic configuration can serve as the dopants to promote the formation of self-trapped excitons,so as to activate highly efficient luminescence.As a re-sult,the as-prepared Sb3+doped(R/S-MBA)3 InCl6 show not only SHG responses but also CPL signals with luminescence dissymmetry factor of−5.3×10^(−3) and 4.7×10^(−3).This work provides a new inspiration for the exploitation of chiral multifunctional materials.展开更多
A chiral phosphorous derivatizing agent prepared from PCl3 and (S)-BINOL was described. It is used to determine the enantiomeric excess of chiral alcohols and amines by 31P NMR.
基金supported by the National Natural Science Foundation of China(21975118,92156014,52373188)。
文摘Versatile stimuli-responsive circularly polarized luminescent(CPL)materials have potential applications in information storage,security encryption,and intelligent displays.In this study,the Z/E isomerization of ultraviolet(UV)-photosensitive achiralα-cyanostilbene derivative was used as an achiral dichroic dye(Switch)to drive the controllable CPL-active response in cholesteric liquid crystals(CLCs).Under irradiation by 365 nm UV light,the resulting CLCs-Z-Switch underwent a Z-to-E configuration isomerization as CLCs-E-Switch,accompanied by a decrease in its dichroic order parameter(SFvalue)from 0.15to 0.07.Although the quantum yield(QY)of CLCs-E-Switch increased from 8.1%(CLCs-Z-Switch)to 16.8%,the corresponding glumvalues of CPL emission decreased from+0.55/-0.57 to+0.37/-0.39 due to a decrease in the order of helical arrangement of E-Switch in E7 media.This study enables photosensitive CLCs-Switch to be applied for optical information storage devices.
文摘Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31%at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.
基金supported by the National Funds for Distinguished Young Scientists(No.61825503)the National Natural Science Foundation of China(Nos.62288102,62375142,22161160318).
文摘Recently,organic-inorganic hybrid metal halides(HMHs)have attracted extensive attention as promis-ing multifunctional materials by virtue of their structural diversity and tunable photophysical properties.However,it remains a challenge to design HMHs with specific functions on demand.Herein,by introduc-ing R/S-methylbenzylamine(R/S-MBA)and doping Sb^(3+),we have achieved both second harmonic gen-eration(SHG)and circularly polarized luminescence(CPL)properties in lead-free indium halides.The introduction of chiral organic cations can break the symmetry and induce the indium halides to crys-tallize in the chiral space group.The Sb^(3+)with ns2 electronic configuration can serve as the dopants to promote the formation of self-trapped excitons,so as to activate highly efficient luminescence.As a re-sult,the as-prepared Sb3+doped(R/S-MBA)3 InCl6 show not only SHG responses but also CPL signals with luminescence dissymmetry factor of−5.3×10^(−3) and 4.7×10^(−3).This work provides a new inspiration for the exploitation of chiral multifunctional materials.
基金We are very grateful for the financial support of the National Natural Science Foundation of China (No.29872016) and the Hong Kong Polytechnic University ASD Fund.
文摘A chiral phosphorous derivatizing agent prepared from PCl3 and (S)-BINOL was described. It is used to determine the enantiomeric excess of chiral alcohols and amines by 31P NMR.