A new silole monomer with two 4-（N,N-dimethylamino）phenyl substitutions on silicon atom as designed and synthesized. Three copolymers PF-N-HPS1, PF-N-HPS10 and PF-N-HPS20 were then obtained by copolymerizations of 2...A new silole monomer with two 4-（N,N-dimethylamino）phenyl substitutions on silicon atom as designed and synthesized. Three copolymers PF-N-HPS1, PF-N-HPS10 and PF-N-HPS20 were then obtained by copolymerizations of 2,7-fluorene deriva- tives with the silole monomer at feed ratios of 1%, 10%, and 20%. Their UV-vis absorption, electrochemical, photolumines- cent, and electroluminescent （EL） properties were investigated. PF-N-HPS possessed HOMO levels of -5.25-5.58 eV, and showed green emissions. Using PF-N-HPS as the emissive layer, three different polymer light-emitting diodes were fabricated as device A with ITO/PEDOT/PF-N-HPS/A1, device B with ITO/PEDOT/PF-N-HPS/Ba/A1, and device C with ITO/PEDOT/ PF-N-HPS/TPBI/Ba/A1. For the device A, PF-N-HPS only showed very low EL efficiency of 0.06-0.33 cd/A, indicating that the A1 cathode could not inject electron efficiently to the emissive polymers containing the 4-（N,N-dimethylamino）phenyl groups. For the device B, low work function Ba supplied better electron injections, and the EL efficiency could be improved to 0.85-1.44 cd/A. TPBI with a deep HOMO level of -6.2 eV could enhance electron transport and hole blocking. Thus modi- fied recombinations and largely elevated EL efficiency of 4.56-7.96 cd/A were achieved for the device C. The separation of the emissive layer and metal cathode with the TPBI layer may also suppress exciton quenching at the cathode interface.展开更多
Efficient synthesis and resolution of a series of meta-substituted inherently chiral aminocalix[4]arene derivatives have been described. Consequently,the meta-nitro,bromo and chloro substituted inherently chiral calix...Efficient synthesis and resolution of a series of meta-substituted inherently chiral aminocalix[4]arene derivatives have been described. Consequently,the meta-nitro,bromo and chloro substituted inherently chiral calix[4]arenes could be directly synthesized by the nitration,bromination,and chlorination of the acylating product of aminocalix[4]arene. meta-Cyano and phenyl substituted inherently chiral aminocalix[4]arenes were readily obtained by the nucleophilic substitution reaction or Suzuki coupling reaction from the meta-bromo substituted one under the Pd-catalyzed conditions. For kinetic resolution of the racemic inherently chiral aminocalix[4]arenes,it was found that the electron-withdrawing ability of substituent was helpful to improving the resolution efficiency of the acylation process,and the kinetic resolution could be efficiently applied to the resolution of meta-nitro substituted inherently chiral aminocalix[4]arene,providing (cS)-or (cR)-isomer in up to 95% or 99.9% ee value,respectively,with the corresponding chiral acylating reagent. Moreover,by introduction of the chiral auxiliary,enantiopure antipodes of meta-cyano and phenyl substituted inherently chiral aminocalix[4]arenes could also be readily obtained. These enantiopure amino-calix[4]arenes are potential building blocks for constructing novel chiral receptors and asymmetric catalysts.展开更多
Two new fused ring electron acceptors(FREAs)IDT-IC-T and IDT-IC-B with thienyl or phenyl substituents at the terminal INCN unit are synthesized.Theoretical calculations indicate that the two acceptors dominantly favor...Two new fused ring electron acceptors(FREAs)IDT-IC-T and IDT-IC-B with thienyl or phenyl substituents at the terminal INCN unit are synthesized.Theoretical calculations indicate that the two acceptors dominantly favor an intermolecularπ-πstacking between the flanking terminal groups.The twist angle between the aryl substituent and INCN unit has a significant influence on theπ-πstacking distance of terminal unit.IDT-IC-T with a smaller twist angle has a shorterπ-πstacking distance than that of IDT-IC-B with a larger twist angle.In addition,extending the conjugation also affects the blend film morphology.IDT-IC-T and IDT-IC-B based photoactive films show appropriate nanoscale phase separations;whereas,blend films based on the parent compound IDT-IC show large-size acceptor domains.As expected,PBDB-T:IDT-IC-T blend films show higher and more balanced electron and hole mobilities.Moreover,these two acceptors present a good charge-transport connectivity arising from the extended conjugation and the increased intermolecular overlapping.Ultimately,IDT-IC-T demonstrates the highest electron mobility(1.47×10^(-4)cm^2V^(-1)s^(-1))and the best power conversion efficiency(PCE)of 9.43%.As for IDT-IC,which only shows an electron mobility of 7.33×10^(-5)cm^2V^(-1)s^(-1)and a PCE of 5.82%.These findings provide a facile and effective way to improve the photovoltaic performance.展开更多
Phosphorylurea molecules, which contain both phosphoryl and carbonyl groups, are considered efficient extractants for UO_2^(2+). This study aims to explain the complexation of UO_2^(2+)with carbamoylphosphoramidic aci...Phosphorylurea molecules, which contain both phosphoryl and carbonyl groups, are considered efficient extractants for UO_2^(2+). This study aims to explain the complexation of UO_2^(2+)with carbamoylphosphoramidic acid(CPO), a simple model for phosphorylurea, for ligand design for uranium recovery from seawater using density functional theory calculations, natural bond order analysis,and the quantum theory of atoms in molecules. The results showed that, when CPO acts as a monodentate ligand, the affinity of phosphoryl for UO_2^(2+)is stronger than that of carbonyl, and CPO coordinates with UO_2^(2+)through the phosphoryl oxygen atom. When CPO serves as a bidentate ligand, both the phosphoryl and carbonyl oxygen atoms connect to UO_2^(2+), and the U–O(carbonyl) bond plays a more important role than the U–O(phosphoryl) bond in the interaction between UO_2^(2+)and CPO. This paradox may be caused by the significant charge transfer from the U–O(carbonyl) p bond orbital to the C–N σ antibond orbital of the bidentate CPO. The NH spacer between the phosphoryl and carbonyl groups could ensure the delocalization of the electron system of the molecule. The bidentate binding motif is favored by entropy and opposed by enthalpy, while the monodentate binding motif is favored by enthalpy and opposed by entropy. Ultimately, the bidentate binding motif is more favorable than the monodentate one. As expected, the interaction between UO_2^(2+)and the deprotonated CPO is stronger than that between UO_2^(2+)and the neutral CPO. Comparing the interaction between UO_2^(2+)and CPO with that between UO_2^(2+)and Nphenylcarbamoylphosphoramidic acid(Ph CPO), formed by replacing one hydrogen atom from the terminal nitrogen atom of CPO with a phenyl group, the phenyl substituent at the terminal nitrogen atom of Ph CPO shows a slightly negative effect on the interaction between UO_2^(2+)and Ph CPO.展开更多
基金supported by the National Natural Science Foundation of China (21225418,51003080)the National Basic Research Program of China (2013CB834705)+2 种基金the Youth Science Plan for Light of the Morning Sun of Wuhan City (201271031385)State Key Laboratory of Luminescent Materials and Devices (2012-09)Natural Science Foundation of Hubei Province (2012FFB04705)
文摘A new silole monomer with two 4-（N,N-dimethylamino）phenyl substitutions on silicon atom as designed and synthesized. Three copolymers PF-N-HPS1, PF-N-HPS10 and PF-N-HPS20 were then obtained by copolymerizations of 2,7-fluorene deriva- tives with the silole monomer at feed ratios of 1%, 10%, and 20%. Their UV-vis absorption, electrochemical, photolumines- cent, and electroluminescent （EL） properties were investigated. PF-N-HPS possessed HOMO levels of -5.25-5.58 eV, and showed green emissions. Using PF-N-HPS as the emissive layer, three different polymer light-emitting diodes were fabricated as device A with ITO/PEDOT/PF-N-HPS/A1, device B with ITO/PEDOT/PF-N-HPS/Ba/A1, and device C with ITO/PEDOT/ PF-N-HPS/TPBI/Ba/A1. For the device A, PF-N-HPS only showed very low EL efficiency of 0.06-0.33 cd/A, indicating that the A1 cathode could not inject electron efficiently to the emissive polymers containing the 4-（N,N-dimethylamino）phenyl groups. For the device B, low work function Ba supplied better electron injections, and the EL efficiency could be improved to 0.85-1.44 cd/A. TPBI with a deep HOMO level of -6.2 eV could enhance electron transport and hole blocking. Thus modi- fied recombinations and largely elevated EL efficiency of 4.56-7.96 cd/A were achieved for the device C. The separation of the emissive layer and metal cathode with the TPBI layer may also suppress exciton quenching at the cathode interface.
基金supported by the National Natural Science Foundation of China (20625206)the National Basic Research Program of China (2008CB617501,2009ZX09501-018),and the Chinese Academy of Sciences
文摘Efficient synthesis and resolution of a series of meta-substituted inherently chiral aminocalix[4]arene derivatives have been described. Consequently,the meta-nitro,bromo and chloro substituted inherently chiral calix[4]arenes could be directly synthesized by the nitration,bromination,and chlorination of the acylating product of aminocalix[4]arene. meta-Cyano and phenyl substituted inherently chiral aminocalix[4]arenes were readily obtained by the nucleophilic substitution reaction or Suzuki coupling reaction from the meta-bromo substituted one under the Pd-catalyzed conditions. For kinetic resolution of the racemic inherently chiral aminocalix[4]arenes,it was found that the electron-withdrawing ability of substituent was helpful to improving the resolution efficiency of the acylation process,and the kinetic resolution could be efficiently applied to the resolution of meta-nitro substituted inherently chiral aminocalix[4]arene,providing (cS)-or (cR)-isomer in up to 95% or 99.9% ee value,respectively,with the corresponding chiral acylating reagent. Moreover,by introduction of the chiral auxiliary,enantiopure antipodes of meta-cyano and phenyl substituted inherently chiral aminocalix[4]arenes could also be readily obtained. These enantiopure amino-calix[4]arenes are potential building blocks for constructing novel chiral receptors and asymmetric catalysts.
基金supported by the National Natural Science Fundation of China (21574013, 51673028)the Fundamental Research Funds for the Central Universities
文摘Two new fused ring electron acceptors(FREAs)IDT-IC-T and IDT-IC-B with thienyl or phenyl substituents at the terminal INCN unit are synthesized.Theoretical calculations indicate that the two acceptors dominantly favor an intermolecularπ-πstacking between the flanking terminal groups.The twist angle between the aryl substituent and INCN unit has a significant influence on theπ-πstacking distance of terminal unit.IDT-IC-T with a smaller twist angle has a shorterπ-πstacking distance than that of IDT-IC-B with a larger twist angle.In addition,extending the conjugation also affects the blend film morphology.IDT-IC-T and IDT-IC-B based photoactive films show appropriate nanoscale phase separations;whereas,blend films based on the parent compound IDT-IC show large-size acceptor domains.As expected,PBDB-T:IDT-IC-T blend films show higher and more balanced electron and hole mobilities.Moreover,these two acceptors present a good charge-transport connectivity arising from the extended conjugation and the increased intermolecular overlapping.Ultimately,IDT-IC-T demonstrates the highest electron mobility(1.47×10^(-4)cm^2V^(-1)s^(-1))and the best power conversion efficiency(PCE)of 9.43%.As for IDT-IC,which only shows an electron mobility of 7.33×10^(-5)cm^2V^(-1)s^(-1)and a PCE of 5.82%.These findings provide a facile and effective way to improve the photovoltaic performance.
基金supported by the National Natural Science Foundation of China(Nos.21676291,21406272,21571185,and 11605273)the Shanghai Sailing Program(No.16YF1408500)the Jiangsu Planned Projects for Postdoctoral Research Funds(No.1402060B)
文摘Phosphorylurea molecules, which contain both phosphoryl and carbonyl groups, are considered efficient extractants for UO_2^(2+). This study aims to explain the complexation of UO_2^(2+)with carbamoylphosphoramidic acid(CPO), a simple model for phosphorylurea, for ligand design for uranium recovery from seawater using density functional theory calculations, natural bond order analysis,and the quantum theory of atoms in molecules. The results showed that, when CPO acts as a monodentate ligand, the affinity of phosphoryl for UO_2^(2+)is stronger than that of carbonyl, and CPO coordinates with UO_2^(2+)through the phosphoryl oxygen atom. When CPO serves as a bidentate ligand, both the phosphoryl and carbonyl oxygen atoms connect to UO_2^(2+), and the U–O(carbonyl) bond plays a more important role than the U–O(phosphoryl) bond in the interaction between UO_2^(2+)and CPO. This paradox may be caused by the significant charge transfer from the U–O(carbonyl) p bond orbital to the C–N σ antibond orbital of the bidentate CPO. The NH spacer between the phosphoryl and carbonyl groups could ensure the delocalization of the electron system of the molecule. The bidentate binding motif is favored by entropy and opposed by enthalpy, while the monodentate binding motif is favored by enthalpy and opposed by entropy. Ultimately, the bidentate binding motif is more favorable than the monodentate one. As expected, the interaction between UO_2^(2+)and the deprotonated CPO is stronger than that between UO_2^(2+)and the neutral CPO. Comparing the interaction between UO_2^(2+)and CPO with that between UO_2^(2+)and Nphenylcarbamoylphosphoramidic acid(Ph CPO), formed by replacing one hydrogen atom from the terminal nitrogen atom of CPO with a phenyl group, the phenyl substituent at the terminal nitrogen atom of Ph CPO shows a slightly negative effect on the interaction between UO_2^(2+)and Ph CPO.
