Recently,increasing atte ntion has been paid on extending theπ-conjugation structures ofviologens(1,1’-disubstituted-4,4’-bipyridylium salts)by incorporating planar aromatic units into the bipyridinium backbones.Va...Recently,increasing atte ntion has been paid on extending theπ-conjugation structures ofviologens(1,1’-disubstituted-4,4’-bipyridylium salts)by incorporating planar aromatic units into the bipyridinium backbones.Various viologen derivative s with extendedπ-conjugation structures have been synthesized,including the N-termini aromatic substituted viologens,the extendedπ-conjugated viologens(denoted as ECVs)as well as theπ-conjugated oligomeric viologens(denoted as COVs).These compounds typically exhibit interesting properties distinguished from those of an isolated viologen unit,which make them as new class of electron deficient supra-/molecular building blocks in supramolecular chemistry and materials science.In this review,we would like to highlight the recent advances of viologen derivatives with extendedπ-conjugation structures in versatile applications ranging from electrochromic and energy storage materials,the ECV/COV-based supramolecular self-assembly systems including the linear supramolecular polymers and 2D/3D supramolecular organic frameworks(SOFs),to the viologen-based covalent organic frameworks(COFs)/networks.We hope this review will serve as an in-time summary worthy of referring,more importantly,to provide inspiration in the rational design of novel molecules with unexplored properties and functions.展开更多
Perfluorooctanoic acid(PFOA),a persistent environmental pollutant,poses serious health risks and remains challenging to detect due to its low light absorption and weak binding affinity.Luminescence sensing offers a po...Perfluorooctanoic acid(PFOA),a persistent environmental pollutant,poses serious health risks and remains challenging to detect due to its low light absorption and weak binding affinity.Luminescence sensing offers a powerful approach to its rapid and quantitative detection,with electron transfer playing a critical role when energy transfer is limited by the analyte’s unfavorable energy-level alignment.Lanthanidebased metal–organic frameworks(MOFs),featuring sharp emissions,long-lived excited states,and tunable electronic structures,are particularly promising for such applications owing to their ability to precisely regulate electron transfer pathways through structural modulation.However,the impact of the coordination mode and symmetry on sensing performance remains poorly understood due to its complex mechanisms.Herein,we report a series of eight europiumbased MOFs,Eu_(2)(FDA)_(3)(solvent)x,synthesized using a single ligand to enable systematic investigation of the relationship between Eu^(3+) coordination symmetry and PFOA sensing behavior.Notably,MOFs with lower coordination symmetry exhibit significantly higher quenching efficiency due to increased energy-level splitting that promotes electron transfer.This study establishes a clear structurefunction correlation and provides valuable insights for the rational design of MOF-based sensors targeting spectroscopically challenging contaminants,thereby deepening the understanding of luminescence sensing mechanisms based on structure-driven signal transduction processes.展开更多
Isomerism is an essential and widespread phenomenon in organic chemistry but rarely observed in covalent organic frameworks(COFs),a novel class of crystalline porous organic polymers with versatile applications.Herein...Isomerism is an essential and widespread phenomenon in organic chemistry but rarely observed in covalent organic frameworks(COFs),a novel class of crystalline porous organic polymers with versatile applications.Herein,we give an account of the first example of a controllable synthesis of constitutional isomers of a COF.The two isomers exhibited marked differences in their gas/vapor adsorption behaviors and chemical stability in various solvents.Furthermore,structure transformation from one isomer to the other was realized.This work not only paves the way for rational design and synthesis of COF isomers but also provides a vivid example of structure–property relationship in crystalline porous polymers.展开更多
CONSPECTUS:This Account aims to concisely summarize recent advancements in the field of photocatalysis,with a particular focus on dimension-reduced metal−organic nanomaterials,including coordination cages and 2D struc...CONSPECTUS:This Account aims to concisely summarize recent advancements in the field of photocatalysis,with a particular focus on dimension-reduced metal−organic nanomaterials,including coordination cages and 2D structures.Metal−organic frameworks(MOFs),known for their high crystallinity,porosity,and well-determined structures,are at the forefront of this research.They offer a unique confined environment that is optimal for enhancing host−vip interactions.展开更多
基金the Natural Science Foundation of Zhejiang Province(No.LY20B020005)Shanghai Scientific and Technological Innovation Project(No.18JC1410600)for the financial support。
文摘Recently,increasing atte ntion has been paid on extending theπ-conjugation structures ofviologens(1,1’-disubstituted-4,4’-bipyridylium salts)by incorporating planar aromatic units into the bipyridinium backbones.Various viologen derivative s with extendedπ-conjugation structures have been synthesized,including the N-termini aromatic substituted viologens,the extendedπ-conjugated viologens(denoted as ECVs)as well as theπ-conjugated oligomeric viologens(denoted as COVs).These compounds typically exhibit interesting properties distinguished from those of an isolated viologen unit,which make them as new class of electron deficient supra-/molecular building blocks in supramolecular chemistry and materials science.In this review,we would like to highlight the recent advances of viologen derivatives with extendedπ-conjugation structures in versatile applications ranging from electrochromic and energy storage materials,the ECV/COV-based supramolecular self-assembly systems including the linear supramolecular polymers and 2D/3D supramolecular organic frameworks(SOFs),to the viologen-based covalent organic frameworks(COFs)/networks.We hope this review will serve as an in-time summary worthy of referring,more importantly,to provide inspiration in the rational design of novel molecules with unexplored properties and functions.
基金supported by the Robert A.Welch Foundation through an endowed chair(grant no.A-0030)to H.-C.Z.the National Natural Science Foundation of China(grant nos.22471130,22261132509,22435002,and 22121005).
文摘Perfluorooctanoic acid(PFOA),a persistent environmental pollutant,poses serious health risks and remains challenging to detect due to its low light absorption and weak binding affinity.Luminescence sensing offers a powerful approach to its rapid and quantitative detection,with electron transfer playing a critical role when energy transfer is limited by the analyte’s unfavorable energy-level alignment.Lanthanidebased metal–organic frameworks(MOFs),featuring sharp emissions,long-lived excited states,and tunable electronic structures,are particularly promising for such applications owing to their ability to precisely regulate electron transfer pathways through structural modulation.However,the impact of the coordination mode and symmetry on sensing performance remains poorly understood due to its complex mechanisms.Herein,we report a series of eight europiumbased MOFs,Eu_(2)(FDA)_(3)(solvent)x,synthesized using a single ligand to enable systematic investigation of the relationship between Eu^(3+) coordination symmetry and PFOA sensing behavior.Notably,MOFs with lower coordination symmetry exhibit significantly higher quenching efficiency due to increased energy-level splitting that promotes electron transfer.This study establishes a clear structurefunction correlation and provides valuable insights for the rational design of MOF-based sensors targeting spectroscopically challenging contaminants,thereby deepening the understanding of luminescence sensing mechanisms based on structure-driven signal transduction processes.
基金the National Science Fund for Distinguished Young Scholars of China(no.21725404)Shanghai Scientific and Technological Innovation Project(18JC1410600)the Strategic Priority Research Program of the Chinese Academy of Sciences(grant no.XDB20000000)for financial support.
文摘Isomerism is an essential and widespread phenomenon in organic chemistry but rarely observed in covalent organic frameworks(COFs),a novel class of crystalline porous organic polymers with versatile applications.Herein,we give an account of the first example of a controllable synthesis of constitutional isomers of a COF.The two isomers exhibited marked differences in their gas/vapor adsorption behaviors and chemical stability in various solvents.Furthermore,structure transformation from one isomer to the other was realized.This work not only paves the way for rational design and synthesis of COF isomers but also provides a vivid example of structure–property relationship in crystalline porous polymers.
基金supported by the Robert A.Welch Foundation through a Welch Endowed Chair to H.-C.Z.(A0030).
文摘CONSPECTUS:This Account aims to concisely summarize recent advancements in the field of photocatalysis,with a particular focus on dimension-reduced metal−organic nanomaterials,including coordination cages and 2D structures.Metal−organic frameworks(MOFs),known for their high crystallinity,porosity,and well-determined structures,are at the forefront of this research.They offer a unique confined environment that is optimal for enhancing host−vip interactions.
