In nature,enzymes at specific folded conformations exhibit high substrate complementarity,enabling them to efficiently and selectively catalyze biochemical reactions.Inspired by enzymes,coordination cages with conform...In nature,enzymes at specific folded conformations exhibit high substrate complementarity,enabling them to efficiently and selectively catalyze biochemical reactions.Inspired by enzymes,coordination cages with conformational dynamics have been designed and are receiving increasing attention due to their versatile applications in allosteric vip binding and catalysis.We present here two enzyme-mimicking adaptive macrocycle-based coordination cages,Pd_(2)L_(2)^(1) and Pd_(2)L_(2)^(2),from macrocycle-based ligands(L^(1) and L^(2))and the encapsulation and stabilization of Lindqvist polyoxometalates anions M6O192−(M=W or Mo)in neutral aqueous solution.X-ray crystallographic studies have verified the formation of 1:1 host-vip complexes of two Pd_(2)L_(2) cages and the W6O192−anion,via an induced-fit folding mechanism.Compared with the free host,Pd_(2)L_(2)^(1) exhibited an induced-fit semi-folded conformation in the inclusion complex,while Pd_(2)L_(2)^(2) adopted an induced-fit fully-folded conformation.Moreover,the Mo_(6)O_(19)⊂Pd_(2)L_(2) host-vip complexes demonstrate high yield and selectivity in the oxidative decontamination reaction of the sulfur mustard simulant,2-chloroethyl ethyl sulfide.This work not only sheds light on the importance of conformational adaptability in enzyme-like systems but also paves the way for protecting labile POM clusters via host-vip encapsulation toward enhanced catalytic performance in aqueous solution.展开更多
Molecular aggregation affects the electronic interactions between molecules and has emerged as a powerful tool in material science.Aggregate effect finds wide applications in the research of new physical phenomena;how...Molecular aggregation affects the electronic interactions between molecules and has emerged as a powerful tool in material science.Aggregate effect finds wide applications in the research of new physical phenomena;however,its value for chemical reaction development has been far less explored.Herein,we report the development of aggregation-enabled alkene insertion into carbon–halogen bonds.The spontaneous cleavage of C–X(X=Cl,Br,or I)bonds generates an intimate ion pair,which can be quickly captured by alkenes in an aggregated state.Additional catalysts or promoters are not necessary under such circumstances,and solvent quenching experiments indicate that the aggregated state is critical for achieving such sequences.The ionic insertion mode is supported by mechanistic studies,density functional theory calculations,and symmetry-adapted perturbation theory analysis.Results also show that the non-aggregated state may quench the transition state and terminate the insertion process.展开更多
基金supported by the National Key Research and Development Program of China(2022YFA1503300,2021YFA1500400)the National Natural Science Foundation of China(22171262,22171264,22201285)the Science Foundation of Fujian Province(2021J01516,2021J02016).
文摘In nature,enzymes at specific folded conformations exhibit high substrate complementarity,enabling them to efficiently and selectively catalyze biochemical reactions.Inspired by enzymes,coordination cages with conformational dynamics have been designed and are receiving increasing attention due to their versatile applications in allosteric vip binding and catalysis.We present here two enzyme-mimicking adaptive macrocycle-based coordination cages,Pd_(2)L_(2)^(1) and Pd_(2)L_(2)^(2),from macrocycle-based ligands(L^(1) and L^(2))and the encapsulation and stabilization of Lindqvist polyoxometalates anions M6O192−(M=W or Mo)in neutral aqueous solution.X-ray crystallographic studies have verified the formation of 1:1 host-vip complexes of two Pd_(2)L_(2) cages and the W6O192−anion,via an induced-fit folding mechanism.Compared with the free host,Pd_(2)L_(2)^(1) exhibited an induced-fit semi-folded conformation in the inclusion complex,while Pd_(2)L_(2)^(2) adopted an induced-fit fully-folded conformation.Moreover,the Mo_(6)O_(19)⊂Pd_(2)L_(2) host-vip complexes demonstrate high yield and selectivity in the oxidative decontamination reaction of the sulfur mustard simulant,2-chloroethyl ethyl sulfide.This work not only sheds light on the importance of conformational adaptability in enzyme-like systems but also paves the way for protecting labile POM clusters via host-vip encapsulation toward enhanced catalytic performance in aqueous solution.
基金National Natural Science Foundation of China,Grant/Award Numbers:91940305,21933009,81874181,22271195,21871284Natural Science Foundation of Fujian Province,Grant/Award Number:2021J01525+3 种基金Major Scientific and Technological Special Project for“Significant New Drugs Creation”,Grant/Award Number:2019ZX09301158The Emerging Frontier Program of Hospital Development Centre,Grant/Award Number:SHDC12018107Shanghai Science and Technology Development Fund from Central Leading Local Government,Grant/Award Number:YDZX20223100001004Shanghai Municipal Health Commission/Shanghai Municipal Administration of Traditional Chinese Medicine,Grant/Award Number:ZY(2021-2023)−0501。
文摘Molecular aggregation affects the electronic interactions between molecules and has emerged as a powerful tool in material science.Aggregate effect finds wide applications in the research of new physical phenomena;however,its value for chemical reaction development has been far less explored.Herein,we report the development of aggregation-enabled alkene insertion into carbon–halogen bonds.The spontaneous cleavage of C–X(X=Cl,Br,or I)bonds generates an intimate ion pair,which can be quickly captured by alkenes in an aggregated state.Additional catalysts or promoters are not necessary under such circumstances,and solvent quenching experiments indicate that the aggregated state is critical for achieving such sequences.The ionic insertion mode is supported by mechanistic studies,density functional theory calculations,and symmetry-adapted perturbation theory analysis.Results also show that the non-aggregated state may quench the transition state and terminate the insertion process.
