A new kind of hydrazone (I) diastereoisomers was prepared with enantiomeric hydazide (II) and chiral cluster (III), which was characterized by HMBC. Unfortunately, the mixture could not be separated into pure diastere...A new kind of hydrazone (I) diastereoisomers was prepared with enantiomeric hydazide (II) and chiral cluster (III), which was characterized by HMBC. Unfortunately, the mixture could not be separated into pure diastereoisomer. This could be a direction to separate the racemic chiral clusters.展开更多
Amylose tris (phenylcarbamate) chiral stationary phase (ATPC-CSP) was prepared and used for optical resolution of clusters 1 and 2. n-Hexane/2-propanol ( 99/1; v/v) were found to be the most suitable mobile phase on ...Amylose tris (phenylcarbamate) chiral stationary phase (ATPC-CSP) was prepared and used for optical resolution of clusters 1 and 2. n-Hexane/2-propanol ( 99/1; v/v) were found to be the most suitable mobile phase on ATPC-CSP.展开更多
A series of novel chiral tetrahedral heterometal clusters have firstly been separated on cellulose tris-(3,5-dimethylphenylcarbamate) stationary phase by high performance liquid chrom-atography, using hexane as the mo...A series of novel chiral tetrahedral heterometal clusters have firstly been separated on cellulose tris-(3,5-dimethylphenylcarbamate) stationary phase by high performance liquid chrom-atography, using hexane as the mobile phase with various alcohols as modifiers.展开更多
The efficient chiral Ru 3(CO) 12 systems were prepared in situ from Ru 3(CO) 12 and various chiral diimino-or diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hy...The efficient chiral Ru 3(CO) 12 systems were prepared in situ from Ru 3(CO) 12 and various chiral diimino-or diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu 3(CO) 11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru 3 framework.展开更多
The new chiral cluster [NiRuMo(CO)5(m3-S)(h5-C5H5)(h5-C5H4COCH3)] 3 was synthesized by the reaction of precursor [CoRuMo(CO)8(m3-S)(h5-C5H4COCH3)] 1 with NiCp2 2 in refluxing THF. It was characterized by C/H elemental...The new chiral cluster [NiRuMo(CO)5(m3-S)(h5-C5H5)(h5-C5H4COCH3)] 3 was synthesized by the reaction of precursor [CoRuMo(CO)8(m3-S)(h5-C5H4COCH3)] 1 with NiCp2 2 in refluxing THF. It was characterized by C/H elemental analysis, IR and 1H NMR. Molecular structure of cluster 3 was determined by single-crystal X-ray analyses. Crystal data: triclinic, space group P with the following crystallographic parameters: a = 7.9606(8), b = 8.5604(9), c = 14.779(2) , a = 93.908(2), b = 105.057(2), g = 101.463(2)? C17H12O6MoNiRuS, Mr = 600.05, Z = 2, V = 945.5(2) 3, Dc = 2.108 g/cm3, m = 2.568 mm-1, (2q )max ≤ 56.48, F(000) = 584,the final R = 0.0380 and wR = 0.0674 for 2995 observed reflections with I > 2.00s(I).展开更多
Chiral metal-organic clusters(cMOCs)are characterized by diverse chiral origins,tunable luminescence,and multifunctionality.Among them,chiral aluminum oxo clusters(AlOCs)exhibit unique advantages in terms of resource ...Chiral metal-organic clusters(cMOCs)are characterized by diverse chiral origins,tunable luminescence,and multifunctionality.Among them,chiral aluminum oxo clusters(AlOCs)exhibit unique advantages in terms of resource sustainability and environmental friendliness compared to other cluster materials.Nevertheless,the simultaneous achievement of precise enantiomeric control and optical response within AlOCs remains a critical challenge to be addressed in the field.Herein,we achieve precise control over the transition from chirality to circularly polarized luminescence properties in AlOCs by leveraging their highly flexible and modifiable coordination surfaces through a stepwise ligand functionalization strategy.We employed the Al2cluster as a platform with programmable surface coordination sites and introduced classical chiral L/D-valine molecules.We successfully constructed four pairs of alcohol-coordinated pure chiral enantiomers(AlOC-189-L/D-MeOH,EtOH,PrOH,and PDO).Absolute helical structures can be identified in the supramolecular architectures of clusters,achieving unambiguous chirality transfer from chiral ligands to chiral clusters and further to absolute helical superstructures.Hierarchical ligand modification,endowed with a top-down design paradigm,offers a rational and feasible route to cluster functionalization.Based on the excellent replaceability of the Al_(2)cluster's surface coordination sites,we achieved chiral-luminescent bifunctional coupling by partially substituting the chiral ligands withπ-conjugated naphthyl-based luminophores(HNA/HNN),yielding two new classes of enantiomers(AlOC-190-L/D-HNA and AlOC-190-L/D-HNN)exhibiting bright yellow-green photoluminescence(PL).DFT calculations reveal that this is attributed to a ligand-to-ligand charge transfer(LLCT)luminescence mechanism.Notably,AlOC-190-L/D-HNN exhibited promising circularly polarized luminescence(CPL)activity via the synergy between chiral induction from L/D-valine ligands and intermolecular charge transfer of the HNN ligands.This work not only highlights the highly designable coordination chemistry of AlOC-enabling on-demand integration of specific functionalities through modular ligand substitution-but also establishes a novel"ligand editing"paradigm for developing multifunctional chiral optical materials.展开更多
Amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) coated on a kind of small particle silica gel was pre-pared. On this ADMPC chiral stationary phase (CSP), the direct enantiomeric separation of six novel chiral transi...Amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) coated on a kind of small particle silica gel was pre-pared. On this ADMPC chiral stationary phase (CSP), the direct enantiomeric separation of six novel chiral transi-tion metal tetrahedral clusters has firstly been achieved using n-hexane as the mobile phase containing various al-cohols as modifiers. The effect of mobile phase modifiers and the structural variation of the solutes on their reten-tion factors (k) and resolutions (Rs) were investigated. The result suggests that not only the structure and concentra-tion of alcohol in mobile phase, but also the structural differences in racemates can have a pronounced effect on enantiomeric separation. ADMPC-CSP is a suitable CSP for the optical resolution of chiral tetrahedral cluster by HPLC.展开更多
The development of stimuli-responsive circularly polarized luminescence(CPL)materials is quite attractive but challenging.Here,a pair of atomically precise enan-tiomers R/S-Ag20 nanoclusters has been synthesized using...The development of stimuli-responsive circularly polarized luminescence(CPL)materials is quite attractive but challenging.Here,a pair of atomically precise enan-tiomers R/S-Ag20 nanoclusters has been synthesized using chiral acid ligands.And then,stimuli-responsive CPL materials were developed by assembling the chiral silver nanoclusters with an achiral bridging ligand.The atomically precise silver cluster-assembled materials produce CPL with a dissymmetry factor(|glum|)of 1×10-3,through the high-efficiency chiral induction process.More interestingly,the single CPL band at room temperature could quickly transform into highly separated dual CPL emissions at low temperature.This study provides a new strategy for the rational functionalization of chiral silver clusters in preparing cluster-based CPL emitters and enriches the types of stimuli-responsive CPL materials.展开更多
基金We are grate ful to the National Natural Science Foundation of China for the f inancial support of this work.
文摘A new kind of hydrazone (I) diastereoisomers was prepared with enantiomeric hydazide (II) and chiral cluster (III), which was characterized by HMBC. Unfortunately, the mixture could not be separated into pure diastereoisomer. This could be a direction to separate the racemic chiral clusters.
文摘Amylose tris (phenylcarbamate) chiral stationary phase (ATPC-CSP) was prepared and used for optical resolution of clusters 1 and 2. n-Hexane/2-propanol ( 99/1; v/v) were found to be the most suitable mobile phase on ATPC-CSP.
基金supported by the Chinese Academy of Sciences under a‘Hundreds of Talents program’to Yonmnin Li.
文摘A series of novel chiral tetrahedral heterometal clusters have firstly been separated on cellulose tris-(3,5-dimethylphenylcarbamate) stationary phase by high performance liquid chrom-atography, using hexane as the mobile phase with various alcohols as modifiers.
基金Supported by the National Natural Science Foundation of China(No.2 0 0 730 34,2 0 3730 5 6,2 0 1710 37),Fujian Provinceand Technology Comm ission(No.2 0 0 2 F0 16 ) and Xiamen Science and Technology Com mission(No.35 0 2 Z2 0 0 2 10 4 4 )
文摘The efficient chiral Ru 3(CO) 12 systems were prepared in situ from Ru 3(CO) 12 and various chiral diimino-or diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu 3(CO) 11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru 3 framework.
基金This work was supported by the National Natural Science Foundation of China(29871061)
文摘The new chiral cluster [NiRuMo(CO)5(m3-S)(h5-C5H5)(h5-C5H4COCH3)] 3 was synthesized by the reaction of precursor [CoRuMo(CO)8(m3-S)(h5-C5H4COCH3)] 1 with NiCp2 2 in refluxing THF. It was characterized by C/H elemental analysis, IR and 1H NMR. Molecular structure of cluster 3 was determined by single-crystal X-ray analyses. Crystal data: triclinic, space group P with the following crystallographic parameters: a = 7.9606(8), b = 8.5604(9), c = 14.779(2) , a = 93.908(2), b = 105.057(2), g = 101.463(2)? C17H12O6MoNiRuS, Mr = 600.05, Z = 2, V = 945.5(2) 3, Dc = 2.108 g/cm3, m = 2.568 mm-1, (2q )max ≤ 56.48, F(000) = 584,the final R = 0.0380 and wR = 0.0674 for 2995 observed reflections with I > 2.00s(I).
基金supported by the National Natural Science Foundation of China(22371278,92261108,92061104)the Natural Science Foundation of Fujian Province(2021J06035)+1 种基金the Fujian Provincial Department of Science and Technology(#2023T3081)the Youth Innovation Promotion Association Chinese Academy of Sciences(Y2021081).
文摘Chiral metal-organic clusters(cMOCs)are characterized by diverse chiral origins,tunable luminescence,and multifunctionality.Among them,chiral aluminum oxo clusters(AlOCs)exhibit unique advantages in terms of resource sustainability and environmental friendliness compared to other cluster materials.Nevertheless,the simultaneous achievement of precise enantiomeric control and optical response within AlOCs remains a critical challenge to be addressed in the field.Herein,we achieve precise control over the transition from chirality to circularly polarized luminescence properties in AlOCs by leveraging their highly flexible and modifiable coordination surfaces through a stepwise ligand functionalization strategy.We employed the Al2cluster as a platform with programmable surface coordination sites and introduced classical chiral L/D-valine molecules.We successfully constructed four pairs of alcohol-coordinated pure chiral enantiomers(AlOC-189-L/D-MeOH,EtOH,PrOH,and PDO).Absolute helical structures can be identified in the supramolecular architectures of clusters,achieving unambiguous chirality transfer from chiral ligands to chiral clusters and further to absolute helical superstructures.Hierarchical ligand modification,endowed with a top-down design paradigm,offers a rational and feasible route to cluster functionalization.Based on the excellent replaceability of the Al_(2)cluster's surface coordination sites,we achieved chiral-luminescent bifunctional coupling by partially substituting the chiral ligands withπ-conjugated naphthyl-based luminophores(HNA/HNN),yielding two new classes of enantiomers(AlOC-190-L/D-HNA and AlOC-190-L/D-HNN)exhibiting bright yellow-green photoluminescence(PL).DFT calculations reveal that this is attributed to a ligand-to-ligand charge transfer(LLCT)luminescence mechanism.Notably,AlOC-190-L/D-HNN exhibited promising circularly polarized luminescence(CPL)activity via the synergy between chiral induction from L/D-valine ligands and intermolecular charge transfer of the HNN ligands.This work not only highlights the highly designable coordination chemistry of AlOC-enabling on-demand integration of specific functionalities through modular ligand substitution-but also establishes a novel"ligand editing"paradigm for developing multifunctional chiral optical materials.
基金Project supported by Chinese Academy of Science (No. KY95-S1-205).
文摘Amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) coated on a kind of small particle silica gel was pre-pared. On this ADMPC chiral stationary phase (CSP), the direct enantiomeric separation of six novel chiral transi-tion metal tetrahedral clusters has firstly been achieved using n-hexane as the mobile phase containing various al-cohols as modifiers. The effect of mobile phase modifiers and the structural variation of the solutes on their reten-tion factors (k) and resolutions (Rs) were investigated. The result suggests that not only the structure and concentra-tion of alcohol in mobile phase, but also the structural differences in racemates can have a pronounced effect on enantiomeric separation. ADMPC-CSP is a suitable CSP for the optical resolution of chiral tetrahedral cluster by HPLC.
基金National Natural Science Foundation of China,Grant/Award Number:92061201 U21A20277Thousand Talents(Zhongyuan Scholars)Program of Henan Province,Grant/Award Number:234000510007Excellent Youth Foundation of Henan Scientific Committee,Grant/Award Number:232300421022。
文摘The development of stimuli-responsive circularly polarized luminescence(CPL)materials is quite attractive but challenging.Here,a pair of atomically precise enan-tiomers R/S-Ag20 nanoclusters has been synthesized using chiral acid ligands.And then,stimuli-responsive CPL materials were developed by assembling the chiral silver nanoclusters with an achiral bridging ligand.The atomically precise silver cluster-assembled materials produce CPL with a dissymmetry factor(|glum|)of 1×10-3,through the high-efficiency chiral induction process.More interestingly,the single CPL band at room temperature could quickly transform into highly separated dual CPL emissions at low temperature.This study provides a new strategy for the rational functionalization of chiral silver clusters in preparing cluster-based CPL emitters and enriches the types of stimuli-responsive CPL materials.
