Luminescent cocrystals have been received much attention in fluorescence imaging and sensor application. In this work, we report that the high-quality chiral luminescent cocrystal can be obtained through a molecular s...Luminescent cocrystals have been received much attention in fluorescence imaging and sensor application. In this work, we report that the high-quality chiral luminescent cocrystal can be obtained through a molecular self-assembly process of 2,20-binaphthol and 2-（3-pyridyl）-1 H-benzimidazole. The assembly modes and stacking fashions of as-obtained cocrystal were determined by single crystal X-ray diffractometer. The structure and optical properties of the cocrystals were characterized by fluorescence emission, fluorescence decay, Raman and circular dichroism spectra. The results show that both the pristine co-assembled units（R-BINOL and S-BINOL） give rise to the R conformation within the final cocrystal, suggesting that the formation of cocrystal can be an effective way to achieve R/S-isomeric transformation of 2,20-binaphthol. It is also expected that the co-crystallization approach has much flexibility and potential applications for the design and selective formation of chiral luminescent materials.展开更多
A new chiral bromobinaphthol-pyrene compound was developed to achieve a green circularly polarized luminescence(CPL)from its excimer with a dissymmetry factor(|glum|)value of 4.3×10^-3 and a high quantum yieldΦF...A new chiral bromobinaphthol-pyrene compound was developed to achieve a green circularly polarized luminescence(CPL)from its excimer with a dissymmetry factor(|glum|)value of 4.3×10^-3 and a high quantum yieldΦF,solid up to 55.9%,while no CPL signals could be observed for the blue luminescence from unimolecule.Meanwhile,reversal CPL signals can be observed from both concentrated solution and solid.展开更多
The photophysical behaviors of the oligomer based on 1,1'-binaphthol with3,3'-acetylene spacer were investigated. The oligomer molecule has a naphthyl-acetylene-naphthyl effective conjugation segment. The atro...The photophysical behaviors of the oligomer based on 1,1'-binaphthol with3,3'-acetylene spacer were investigated. The oligomer molecule has a naphthyl-acetylene-naphthyl effective conjugation segment. The atropic of the 1,1'-binaphthyl moiety led totwisted and rigid main chain in the oligomer. With the changes of the external environ-ment such as solvents used, solvent viscosity and ambient temperature, the wavelengthsof absorption and the intensities of fluorescence and absorption are changed slightly, butthe fluorescent intensity and quantum yield can be influenced. The luminescent behav-iors of the oligomer exhibit twisted intramolecular charge transfer characteristics, whichcould have a potential application in wavelength-stable light emitting material adaptableto ambient temperature and the solvents used in wide range.展开更多
The self-assembly of a racemic exo-bidentate ligand 2,2＇-bis（4-pyridylmethyloxy）-1,1＇-binaphthyl, namely Rac-L, with cadmium（Ⅱ） salt gave rise to a new one-dimensional polymer, which has been characterized by s...The self-assembly of a racemic exo-bidentate ligand 2,2＇-bis（4-pyridylmethyloxy）-1,1＇-binaphthyl, namely Rac-L, with cadmium（Ⅱ） salt gave rise to a new one-dimensional polymer, which has been characterized by single crystal X-ray diffraction analysis. The polymer crystallizes in a triclinic space group P-1 with unit cell parameters： a=0.6976（1） nm, b= 1.30160（14） nm, c= 1.71146（17） nrn.α= 105.141（3）°, β=94.263（5）°, γ= 100.405（4）°, V= 1.4633（2） nm^3, Z=2, C32H29CdCl2N2O4.5, M=696.88, Dc= 1.584 g/cm^3, F（000）=708,μ（Mo Kα）=0.972 mm^-1. The final R and wR are 0.0498 and 0.1282 for 5079 observed reflections with I≥2σ（I）.展开更多
Reaction of sulfonylated binaphthol [2-hydroxy-2＇-tosyloxy-l,l-binaphthyl （la, Ts-Binol） or 2-hydroxy-2＇- （phenylsulfonyloxy）-l,l-binaphthyl （lb, Ps-Binol）] with 1 equiv, of ZnEt2 afforded zinc complexes [（Ys...Reaction of sulfonylated binaphthol [2-hydroxy-2＇-tosyloxy-l,l-binaphthyl （la, Ts-Binol） or 2-hydroxy-2＇- （phenylsulfonyloxy）-l,l-binaphthyl （lb, Ps-Binol）] with 1 equiv, of ZnEt2 afforded zinc complexes [（Ys-Binol）ZnEt]2 （2a） and [（Ps-Binol）ZnEt]2 （2b）. Further reaction of zinc complexes 2a and 2b with benzyl alco- hol （BnOH） gave the zinc benzyloxide [（Ts-Binol）2Zn2（OBn）2]2 （3a） and [（Ps-Binol）2Znz（OBn）2]2 （3b）. Alterna- tively, the zinc benzyloxides 3a and 3b could also be obtained by reaction of compound la or lb with Zn（OBn）2 （in situ reaction of ZnEt2 and BnOH）. The complexes were fully characterized by elemental analyses and spectroscopic analyses, and complexes 2a, 2b and 3a were further characterized by single-crystal X-ray analyses. The catalytic activities of these zinc complexes towards ring-opening polymerization of ε-caprolactone and D,L-lactide were studied.展开更多
Four chiral polymers P-1, P-2, P-3 and P-4 were synthesized by the polymerization of （S）-2,2＇-dioctoxy-1,1＇- binaphthyl-6,6＇-boronic acid （S-M-3） with （S）-6,6＇-dibromo-1,1＇-binaphthol （S-M-1）, （R）-6,6＇...Four chiral polymers P-1, P-2, P-3 and P-4 were synthesized by the polymerization of （S）-2,2＇-dioctoxy-1,1＇- binaphthyl-6,6＇-boronic acid （S-M-3） with （S）-6,6＇-dibromo-1,1＇-binaphthol （S-M-1）, （R）-6,6＇-dibromo-1,1＇- binaphthol （R-M-1）, （S）-3,3＇-diiodo-1,1＇-binaphthol （S-M-2） and （R）-3,3＇-diiodo-1,1＇-binaphthol （R-M-2） under Pd-catalyzed Suzuki reaction, respectively. All four polymers can show good solubility in some common solvents due to the nonplanarity of the polymers in the main chain backbone and flexible alkyl groups in the side chain. The analysis results indicate that specific rotation and circular dichroism （CD） spectral signals of the alternative S-S chiral polymers P-1 and P-3 are larger than those of S-R chiral polymers P-2 and P-4, but their UV-Vis and fluorescence spectra are almost similar. The results of asymmetric enantioselectivity of four polymers for diethylzinc addition to benzaldehyde indicate that catalytically active center is （R） or （S）-1, 1＇-binaphthol moieties.展开更多
基金supported by the National Natural Science Foundation of China(NSFC, Nos. 21771021 and 21473013)the National Basic Research Program of China(973 Program, No. 2014CB932103)Beijing Municipal Natural Science Foundation (No. 2152016)
文摘Luminescent cocrystals have been received much attention in fluorescence imaging and sensor application. In this work, we report that the high-quality chiral luminescent cocrystal can be obtained through a molecular self-assembly process of 2,20-binaphthol and 2-（3-pyridyl）-1 H-benzimidazole. The assembly modes and stacking fashions of as-obtained cocrystal were determined by single crystal X-ray diffractometer. The structure and optical properties of the cocrystals were characterized by fluorescence emission, fluorescence decay, Raman and circular dichroism spectra. The results show that both the pristine co-assembled units（R-BINOL and S-BINOL） give rise to the R conformation within the final cocrystal, suggesting that the formation of cocrystal can be an effective way to achieve R/S-isomeric transformation of 2,20-binaphthol. It is also expected that the co-crystallization approach has much flexibility and potential applications for the design and selective formation of chiral luminescent materials.
基金the National Natural Science Foundation of China(NSFC,Nos.21788102,21722603 and 21871083)Shanghai Municipal Science and Technology Major Project(No.2018SHZDZX03)+2 种基金‘Shu Guang’Project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation(No.19SG26)the Innovation Program of Shanghai Municipal Education Commission(No.2017-01-07-00-02-E00010)the Fundamental Research Funds for the Central Universities。
文摘A new chiral bromobinaphthol-pyrene compound was developed to achieve a green circularly polarized luminescence(CPL)from its excimer with a dissymmetry factor(|glum|)value of 4.3×10^-3 and a high quantum yieldΦF,solid up to 55.9%,while no CPL signals could be observed for the blue luminescence from unimolecule.Meanwhile,reversal CPL signals can be observed from both concentrated solution and solid.
基金This work is supported by the National Natural Science Foundation of China and Tulane University
文摘The photophysical behaviors of the oligomer based on 1,1'-binaphthol with3,3'-acetylene spacer were investigated. The oligomer molecule has a naphthyl-acetylene-naphthyl effective conjugation segment. The atropic of the 1,1'-binaphthyl moiety led totwisted and rigid main chain in the oligomer. With the changes of the external environ-ment such as solvents used, solvent viscosity and ambient temperature, the wavelengthsof absorption and the intensities of fluorescence and absorption are changed slightly, butthe fluorescent intensity and quantum yield can be influenced. The luminescent behav-iors of the oligomer exhibit twisted intramolecular charge transfer characteristics, whichcould have a potential application in wavelength-stable light emitting material adaptableto ambient temperature and the solvents used in wide range.
基金Project supported by the National Natural Science Foundation of China （No. 20231020） and the Natural Science Foundation of Fujian Province （No. L2003B01）.
文摘The self-assembly of a racemic exo-bidentate ligand 2,2＇-bis（4-pyridylmethyloxy）-1,1＇-binaphthyl, namely Rac-L, with cadmium（Ⅱ） salt gave rise to a new one-dimensional polymer, which has been characterized by single crystal X-ray diffraction analysis. The polymer crystallizes in a triclinic space group P-1 with unit cell parameters： a=0.6976（1） nm, b= 1.30160（14） nm, c= 1.71146（17） nrn.α= 105.141（3）°, β=94.263（5）°, γ= 100.405（4）°, V= 1.4633（2） nm^3, Z=2, C32H29CdCl2N2O4.5, M=696.88, Dc= 1.584 g/cm^3, F（000）=708,μ（Mo Kα）=0.972 mm^-1. The final R and wR are 0.0498 and 0.1282 for 5079 observed reflections with I≥2σ（I）.
文摘Reaction of sulfonylated binaphthol [2-hydroxy-2＇-tosyloxy-l,l-binaphthyl （la, Ts-Binol） or 2-hydroxy-2＇- （phenylsulfonyloxy）-l,l-binaphthyl （lb, Ps-Binol）] with 1 equiv, of ZnEt2 afforded zinc complexes [（Ys-Binol）ZnEt]2 （2a） and [（Ps-Binol）ZnEt]2 （2b）. Further reaction of zinc complexes 2a and 2b with benzyl alco- hol （BnOH） gave the zinc benzyloxide [（Ts-Binol）2Zn2（OBn）2]2 （3a） and [（Ps-Binol）2Znz（OBn）2]2 （3b）. Alterna- tively, the zinc benzyloxides 3a and 3b could also be obtained by reaction of compound la or lb with Zn（OBn）2 （in situ reaction of ZnEt2 and BnOH）. The complexes were fully characterized by elemental analyses and spectroscopic analyses, and complexes 2a, 2b and 3a were further characterized by single-crystal X-ray analyses. The catalytic activities of these zinc complexes towards ring-opening polymerization of ε-caprolactone and D,L-lactide were studied.
基金Project supported by the National Natural Science Foundation of China （No, 20474028） and Jiangsu Provincial Natural Science Foundation （No BK2004086）.
文摘Four chiral polymers P-1, P-2, P-3 and P-4 were synthesized by the polymerization of （S）-2,2＇-dioctoxy-1,1＇- binaphthyl-6,6＇-boronic acid （S-M-3） with （S）-6,6＇-dibromo-1,1＇-binaphthol （S-M-1）, （R）-6,6＇-dibromo-1,1＇- binaphthol （R-M-1）, （S）-3,3＇-diiodo-1,1＇-binaphthol （S-M-2） and （R）-3,3＇-diiodo-1,1＇-binaphthol （R-M-2） under Pd-catalyzed Suzuki reaction, respectively. All four polymers can show good solubility in some common solvents due to the nonplanarity of the polymers in the main chain backbone and flexible alkyl groups in the side chain. The analysis results indicate that specific rotation and circular dichroism （CD） spectral signals of the alternative S-S chiral polymers P-1 and P-3 are larger than those of S-R chiral polymers P-2 and P-4, but their UV-Vis and fluorescence spectra are almost similar. The results of asymmetric enantioselectivity of four polymers for diethylzinc addition to benzaldehyde indicate that catalytically active center is （R） or （S）-1, 1＇-binaphthol moieties.
