Chiral thermally activated delayed fluorescence(TADF) molecules showing circularly polarized luminescence(CPL) have great potential in 3D displays. However, the relationships among CPL property, device performance and...Chiral thermally activated delayed fluorescence(TADF) molecules showing circularly polarized luminescence(CPL) have great potential in 3D displays. However, the relationships among CPL property, device performance and molecule structure are still not clear. In this article, we develop a strategy to promote dissymmetry factors without sacrifice in device performance and study the impact of molecule structures towards CPL property. Three novel TADF enantiomers are synthesized and studied.(R/S)-SCN with diminutive cyano group as an acceptor shows dissymmetry factor |gPL| ≈ 1.4×10^(-3) and noticeable organic light-emitting diode(OLED) performances with a maximum external quantum efficiency(EQEmax) of 23.0%. For(R/S)-SPHCN, the prolonged electron withdrawing group benzonitrile enhances |gPL| up to 3.6×10^(-3) with decreased device EQEmaxof 15.4%. By further replacing benzonitrile with(trifluoromethyl)pyridine, the enantiomers of(R/S)-SCFPY show similar |gPL| factors of 3.5×10^(-3) and device EQE_(max)up to 23.3%, which represents the highest efficiency among sprio-type TADF materials based OLEDs. Furthermore, the OLEDs also show obvious circularly polarized electroluminescence with gELfactors of-1.4/1.8×10^(-3),-3.6/3.6×10^(-3) and-3.7/3.6×10^(-3), respectively. These results indecate by delicate functional group engineering, high g factor can be achieved while maintaining decent device performances. Besides,(R/S)-SCFPY represents an impressive TADF emitter, which shows promoted g factor and recorded high device EQE_(max)among similar molecules.展开更多
An organocatalytic asymmetric [3+2] cycloaddition of trifluoromethyl-containing azomethine ylides with cyclic 2,4-dienones was developed.The process enables efficient incorporation of CF3 groups into functionalized sp...An organocatalytic asymmetric [3+2] cycloaddition of trifluoromethyl-containing azomethine ylides with cyclic 2,4-dienones was developed.The process enables efficient incorporation of CF3 groups into functionalized spiro [pyrro lid in-3,2'-oxindoles] in high yields with good to excellent enantio-and diastereoselectivities.展开更多
The title compound, spiro[ 1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]- hexane-2,2＇-3＇-（16＇-methoxyacetatyl-4＇-l-menthyloxybutyrolactone）] 1, was obtained via tandem asymmetric double Michael addition/inte...The title compound, spiro[ 1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]- hexane-2,2＇-3＇-（16＇-methoxyacetatyl-4＇-l-menthyloxybutyrolactone）] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-（5H）-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally [letermined by single-crystal X-ray diffraction. Crystal data： C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121. α = 9.6564（7）, b = 14.8994（11）, c = 23.6771（17） A, V= 3406.5（4） A^3, Z = 4, Dc= 1.255 g/cm^3, 2（MoKa） = 0.71073 A,μ= 1.254 mm^-1 and F（000） = 1360. The structure was refined to R =[0.0324 and wR = 0.0737 for 5123 observed reflections （I〉 2σ（I））. The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.展开更多
The title compound, spiro[1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]-hexane-2,2-3-(16-methoxyacetatyl-4-l-menthyloxybutyrolactone)] 1, was obtained via tandem asymmetric double Michael addition/internal nucleop...The title compound, spiro[1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]-hexane-2,2-3-(16-methoxyacetatyl-4-l-menthyloxybutyrolactone)] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-(5H)-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally determined by single-crystal X-ray diffraction. Crystal data: C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121, a = 9.6564(7), b = 14.8994(11), c = 23.6771(17) , V = 3406.5(4) 3, Z = 4, Dc = 1.255 g/cm3, λ(MoKα) = 0.71073 , μ = 1.254 mm-1 and F(000) = 1360. The structure was refined to R = 0.0324 and wR = 0.0737 for 5123 observed reflections (I > 2σ(I)). The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.展开更多
基金supported by the National Natural Science Foundation of China (21975119, 51773088)。
文摘Chiral thermally activated delayed fluorescence(TADF) molecules showing circularly polarized luminescence(CPL) have great potential in 3D displays. However, the relationships among CPL property, device performance and molecule structure are still not clear. In this article, we develop a strategy to promote dissymmetry factors without sacrifice in device performance and study the impact of molecule structures towards CPL property. Three novel TADF enantiomers are synthesized and studied.(R/S)-SCN with diminutive cyano group as an acceptor shows dissymmetry factor |gPL| ≈ 1.4×10^(-3) and noticeable organic light-emitting diode(OLED) performances with a maximum external quantum efficiency(EQEmax) of 23.0%. For(R/S)-SPHCN, the prolonged electron withdrawing group benzonitrile enhances |gPL| up to 3.6×10^(-3) with decreased device EQEmaxof 15.4%. By further replacing benzonitrile with(trifluoromethyl)pyridine, the enantiomers of(R/S)-SCFPY show similar |gPL| factors of 3.5×10^(-3) and device EQE_(max)up to 23.3%, which represents the highest efficiency among sprio-type TADF materials based OLEDs. Furthermore, the OLEDs also show obvious circularly polarized electroluminescence with gELfactors of-1.4/1.8×10^(-3),-3.6/3.6×10^(-3) and-3.7/3.6×10^(-3), respectively. These results indecate by delicate functional group engineering, high g factor can be achieved while maintaining decent device performances. Besides,(R/S)-SCFPY represents an impressive TADF emitter, which shows promoted g factor and recorded high device EQE_(max)among similar molecules.
基金supported by the National Natural Science Foundation of China(Nos.21272068,21572056,21801077)China Postdoctoral Science Foundation(Nos.2017M621382,2018T110355)+1 种基金Shanghai Sailing Program(No.18YF1406200)the Fundamental Research Funds for the Central Universities。
文摘An organocatalytic asymmetric [3+2] cycloaddition of trifluoromethyl-containing azomethine ylides with cyclic 2,4-dienones was developed.The process enables efficient incorporation of CF3 groups into functionalized spiro [pyrro lid in-3,2'-oxindoles] in high yields with good to excellent enantio-and diastereoselectivities.
基金Supported by the National Natural Science Foundation of China (No. 29672004)
文摘The title compound, spiro[ 1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]- hexane-2,2＇-3＇-（16＇-methoxyacetatyl-4＇-l-menthyloxybutyrolactone）] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-（5H）-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally [letermined by single-crystal X-ray diffraction. Crystal data： C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121. α = 9.6564（7）, b = 14.8994（11）, c = 23.6771（17） A, V= 3406.5（4） A^3, Z = 4, Dc= 1.255 g/cm^3, 2（MoKa） = 0.71073 A,μ= 1.254 mm^-1 and F（000） = 1360. The structure was refined to R =[0.0324 and wR = 0.0737 for 5123 observed reflections （I〉 2σ（I））. The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.
文摘The title compound, spiro[1-bromo-4-l-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]-hexane-2,2-3-(16-methoxyacetatyl-4-l-menthyloxybutyrolactone)] 1, was obtained via tandem asymmetric double Michael addition/internal nucleophilic substitution of the chiral synthon, 5-l-menthyloxy-3-bromo-2-(5H)-furanone 2 with methoxy α-chloroacetate as a nucleophile under mild conditions, and structurally determined by single-crystal X-ray diffraction. Crystal data: C31H47BrO9, Mr = 643.60, orthorhombic, space group P212121, a = 9.6564(7), b = 14.8994(11), c = 23.6771(17) , V = 3406.5(4) 3, Z = 4, Dc = 1.255 g/cm3, λ(MoKα) = 0.71073 , μ = 1.254 mm-1 and F(000) = 1360. The structure was refined to R = 0.0324 and wR = 0.0737 for 5123 observed reflections (I > 2σ(I)). The crystallographic results of molecule 1 show that the interesting reaction of 2 with methoxy α-chloroacetate, in the usual manner, gave the spiro-cyclopropane skeleton with O-linked derivative containing multiple stereogenic centers 1 rather than the expected C-linked derivative.
