Realizing circularly polarized luminescence(CPL)with the same chiral direction by chiral luminogenic molecules under the identical conditions is unprecedented.Meanwhile,obtaining circularly polarized phosphorescence(C...Realizing circularly polarized luminescence(CPL)with the same chiral direction by chiral luminogenic molecules under the identical conditions is unprecedented.Meanwhile,obtaining circularly polarized phosphorescence(CPP)with a large dissymmetry factor(g_(lum))is highly significant but rather challenging.Herein,two chiral Au(I)-containing enantiomers,namely(S,S)-1 and(R,R)-1,are prepared.(S,S)-1 and(R,R)-1 show different self-assembly behaviors as the degree of aggregation in solution changes,leading to the formation of a variety of CPP signals.Notably,non-mirror-image CPP,CPP with the high g_(lum) values of+2.78×10^(−2) and−1.54×10^(−2),chirality amplification and inversion from the two chiral Au(I)luminogens are accompanied by the variation of their self-assembly morphologies.Impressively,(S,S)-1 and(R,R)-1 exhibit aggregation-induced CPP with the same chiral direction,and this is the first time that the unidirectional CPL from chiral enantiomers under the identical external environment is observed.Their respective three polymorphic crystals of(S,S)-1 and(R,R)-1,each with different packing arrangements,are fortunately obtained.The polymorphs derived from(S,S)-1 or(R,R)-1 demonstrate both M-helix and P-helix stacking arrangements.Through investigating their CPP properties,stacking modes,and intermolecular interactions of these six types of crystals cultivated by(S,S)-1 and(R,R)-1,the mechanism of their self-assembly morphologies-dependent multiple patterns CPP characteristics of(S,S)-1 and(R,R)-1 is further understood.Additionally,both(S,S)-1 and(R,R)-1 show a force-triggered CPP quenching feature,and the chiral co-assembly system with the|g_(lum)|value reaching 0.11 is gained by a combination of the synthesized enantiomers and commercial achiral liquid crystal.展开更多
Since the concept of aromaticity was first introduced in transition metal complexes,metals have become a crucial component for modulating aromaticity,leading to a variety of structural frameworks.Initial studies succe...Since the concept of aromaticity was first introduced in transition metal complexes,metals have become a crucial component for modulating aromaticity,leading to a variety of structural frameworks.Initial studies successfully achieved aromatic pentalene dianions through metal-ion coordination,and recent advancements in bridgehead metallapentalenes have demonstrated the transformation of antiaromaticity into aromaticity.This research introduces an efficient[2+2+1]cycloaddition strategy with a dual-path cooperative mechanism for constructing the first structurally defined non-aromatic wingtip metallapentalene,including wingtip osmapentalene and its methoxy and hydroxy derivatives.Osmapentalenes display versatile reactivity,allowing for multi-site functionalization via nucleophilic and electrophilic substitutions.Furthermore,the hydroxy derivative easily undergoes a ring-opening reaction with methanol to form osmafuran.The lowest-energy absorption of wingtip osmapentalene falls within the visible range,with adjustable optical and electrochemical properties.展开更多
基金funded by the National Natural Science Foundation of China(22175069 and 22361020)the Academic and Technical Leader Plan of Jiangxi Provincial Main Disciplines(20212BCJ23004).
文摘Realizing circularly polarized luminescence(CPL)with the same chiral direction by chiral luminogenic molecules under the identical conditions is unprecedented.Meanwhile,obtaining circularly polarized phosphorescence(CPP)with a large dissymmetry factor(g_(lum))is highly significant but rather challenging.Herein,two chiral Au(I)-containing enantiomers,namely(S,S)-1 and(R,R)-1,are prepared.(S,S)-1 and(R,R)-1 show different self-assembly behaviors as the degree of aggregation in solution changes,leading to the formation of a variety of CPP signals.Notably,non-mirror-image CPP,CPP with the high g_(lum) values of+2.78×10^(−2) and−1.54×10^(−2),chirality amplification and inversion from the two chiral Au(I)luminogens are accompanied by the variation of their self-assembly morphologies.Impressively,(S,S)-1 and(R,R)-1 exhibit aggregation-induced CPP with the same chiral direction,and this is the first time that the unidirectional CPL from chiral enantiomers under the identical external environment is observed.Their respective three polymorphic crystals of(S,S)-1 and(R,R)-1,each with different packing arrangements,are fortunately obtained.The polymorphs derived from(S,S)-1 or(R,R)-1 demonstrate both M-helix and P-helix stacking arrangements.Through investigating their CPP properties,stacking modes,and intermolecular interactions of these six types of crystals cultivated by(S,S)-1 and(R,R)-1,the mechanism of their self-assembly morphologies-dependent multiple patterns CPP characteristics of(S,S)-1 and(R,R)-1 is further understood.Additionally,both(S,S)-1 and(R,R)-1 show a force-triggered CPP quenching feature,and the chiral co-assembly system with the|g_(lum)|value reaching 0.11 is gained by a combination of the synthesized enantiomers and commercial achiral liquid crystal.
基金the National Natural Science Foundation of China(22175069 and 21772054).
文摘Since the concept of aromaticity was first introduced in transition metal complexes,metals have become a crucial component for modulating aromaticity,leading to a variety of structural frameworks.Initial studies successfully achieved aromatic pentalene dianions through metal-ion coordination,and recent advancements in bridgehead metallapentalenes have demonstrated the transformation of antiaromaticity into aromaticity.This research introduces an efficient[2+2+1]cycloaddition strategy with a dual-path cooperative mechanism for constructing the first structurally defined non-aromatic wingtip metallapentalene,including wingtip osmapentalene and its methoxy and hydroxy derivatives.Osmapentalenes display versatile reactivity,allowing for multi-site functionalization via nucleophilic and electrophilic substitutions.Furthermore,the hydroxy derivative easily undergoes a ring-opening reaction with methanol to form osmafuran.The lowest-energy absorption of wingtip osmapentalene falls within the visible range,with adjustable optical and electrochemical properties.
