The anionic polymerization of N-vinylcarbazole（NVC） by using optically active anionic initiators such as the lithium salts of（S）-1-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-1-FIDH） and（S）-2-（9H...The anionic polymerization of N-vinylcarbazole（NVC） by using optically active anionic initiators such as the lithium salts of（S）-1-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-1-FIDH） and（S）-2-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-2-FIDH） and complexes of（-）-Sparteine with n-butylithium（n-Bu Li-（-）-Sp） or fluorenyl lithium（FILi-（-）-Sp） was achieved. The yield and specific rotation of poly（N-vinylcarbazole）s（poly（NVC）s） were considerably affected by the molar ratio of（S）-FIDH to NVC. The highest yield and specific rotation were obtained with Li-（S）-1-FIDH as an initiator, with a molar ratio of monomer and initiator [M]/[I] = 10/1. The effects of the chiral initiators, type of solvent and the polymerization temperature were investigated. The obtained optical activity of polymers was attributed to asymmetric induction of the chiral initiators.展开更多
A simple synthesis of medicinally important cis-2-methyl-4-azapan-2-one-1,2,3,4-tetrahydroquinolines/cis-9- （2-methyl-l,2,3,4-tetrahydroquinolin-4-yl）-9H-carbazole was reported. Multicomponent one pot synthesis with...A simple synthesis of medicinally important cis-2-methyl-4-azapan-2-one-1,2,3,4-tetrahydroquinolines/cis-9- （2-methyl-l,2,3,4-tetrahydroquinolin-4-yl）-9H-carbazole was reported. Multicomponent one pot synthesis with ani- lines and N-vinylcaprolactam/N-vinyl carbazole via imino Diels-Alder reaction by using antimony trichloride as catalyst and acetonitrile as solvent was employed. NMR technique （2D） was used to study the regio- and stereo- chemistry of newly synthesized compounds. The cis diastereo-selectivity of the products was predicted by COSY and NOESY studies.展开更多
The fluorescence spectra of the poly (N-vinylcarbazole) in solution obtained with chirally organic salts or acid as catalyst or initiator [ (-)Sp: (-)-Sparteine, (+)CSA: D- (+)Camphor-10-sulfonic acid)], respectively,...The fluorescence spectra of the poly (N-vinylcarbazole) in solution obtained with chirally organic salts or acid as catalyst or initiator [ (-)Sp: (-)-Sparteine, (+)CSA: D- (+)Camphor-10-sulfonic acid)], respectively, have been investigated. It is found that the two emission peaks at the longer wavelength (lambda max, ca, 415nm) and the shorter wavelength (lambda max, ca, 370nm) are assigned to the sandwich excimer and second excimer (partial overlap) fluorescence, respectively. The sandwich excimer and partially overlapped excimer are attributed to a fully overlapped structure of neighbouring carbazole chromophores in a totally elipsed conformation of the isotactic sequence, and partially overlapped structure of the syndiotactic sequence. The estimated values of I-415/I-370 and isotactic sequence content by using the fluorescence spectra are in the order: (-)Sp(+) (+)CSA(-)> (+)CSA(-)> (-)Sp(+)ClO(4)(-) (no peak at 415nm for AIBN).展开更多
The redox reaction between N-vinylcarbazole (NVC) and various oxidants including Ce(Ⅳ), Fe(Ⅲ)and benzoylperoxide in methanol proceeds via the initial formation of the NVC N-cation radical which in turn leads to the ...The redox reaction between N-vinylcarbazole (NVC) and various oxidants including Ce(Ⅳ), Fe(Ⅲ)and benzoylperoxide in methanol proceeds via the initial formation of the NVC N-cation radical which in turn leads to the formation of the NVC cyclic dimer, trans-1,2-dicarbazylcyclobutane. Molecular oxygen and a few arylamines are able to accelerate the rate of the formation and increase the yield of the dimer. The mechanism of this process and the functions of oxygen and arylamines are presented as follows: The participation of molecular oxygen is to facilitate the dissociation of the resulting reduced metal ion and the NVC N-cation radical ion pair or charge transfer complex, thereby releasing the free NVC N-cation radical and increase the rate of the formation and yield of the dimer. The arylamine in this reaction between NVC and oxidants can be viewed as electron transfer agent between NVC and the oxidant. Because the amines are present in small amount relative to the oxidants and can be regenerated in process, it is essentially catalytic in nature.展开更多
The organic salts as initiators [A*B-+(-):Ph*3C+ClO4-, Ph(3)*C+SbCl6-, (-)Sp*(ClO4-)-Cl-+ and (-)(Sp)(2)*(+3)(ClO4-)(3)] and catalysts [A(+)B*(-):(+)CSA*, A*B-+*(-):Ph(3)*C+(+)CSA*(-) and (-)Sp*(+)(+)CSA*] are prepare...The organic salts as initiators [A*B-+(-):Ph*3C+ClO4-, Ph(3)*C+SbCl6-, (-)Sp*(ClO4-)-Cl-+ and (-)(Sp)(2)*(+3)(ClO4-)(3)] and catalysts [A(+)B*(-):(+)CSA*, A*B-+*(-):Ph(3)*C+(+)CSA*(-) and (-)Sp*(+)(+)CSA*] are prepared and characterized by specific rotation. The asymmetrically stereoselective induction of the initiators and catalysts in thc polymerization of N-vinylcarbazole is in an order of A*B-+*(-) > A(+)B*(-) > A*B-+(-). The specific rotations of obtained poly(N-vinylcarbazole) (PVCZ) generally are in accordance with mentioned order.展开更多
A kind of non-conjugated polymer memory material, poly（N-vinylcarbazole）, is used to investigate silicon-based storage performance with the fact that the one-bit storage cell circuit consists of a sandwiched indium-...A kind of non-conjugated polymer memory material, poly（N-vinylcarbazole）, is used to investigate silicon-based storage performance with the fact that the one-bit storage cell circuit consists of a sandwiched indium-tin- oxide/poly（N-vinylcarbazole）/Al and an n-type metal-oxide-semiconductor field effect transistor. The memristor on the basis of a nano poly（N-vinylcarbazole） film exhibits electrical bistability and flash memory features, for which the switching-on voltage is -1 V and the on/off current ratio approaches 104. At ambient temperature, the memory circuit possesses higher reliability within the programming time 104 s. The output voltage is dose to 0.5 V during logic 1, while it is approximately 14mV in the logic 0. This paves the way for the study on the technology concerning the binary encoding and data storage of nonvolatile memories.展开更多
A new PVK-based photorefractive polymer composite sensitized by C60 and doped with a higher content of EO chromophore was prepared. The high optical quality thin-film was formed between two ITOcovered glass electrode...A new PVK-based photorefractive polymer composite sensitized by C60 and doped with a higher content of EO chromophore was prepared. The high optical quality thin-film was formed between two ITOcovered glass electrodes. Two-beam-coupling (2BC) experiment was performed by using a He-Ne laser (at wavelength 632.8nm), and an obvious photorefractive performance was observed. The dependence of two-beamcoupling gain coefficient on the applied poling dc electric field was measured.展开更多
Double-layer organic electroluminescent devices have been constructed. A new fluorescent dye, 9,10-bis(phenylethynyl)anthracence, was chosen as the dopant which was molecularly dispersed in the polymer film, and green...Double-layer organic electroluminescent devices have been constructed. A new fluorescent dye, 9,10-bis(phenylethynyl)anthracence, was chosen as the dopant which was molecularly dispersed in the polymer film, and green light was observed from the device with luminance of 130cd/m(2) at 17V.展开更多
基金financially supported by the open project program of Key Laboratory of Environmentally Friendly ChemistryApplications of the Ministry of Education,China(No.09HJYH04)Xiangtan University Doctoral Scientific Research Fund
文摘The anionic polymerization of N-vinylcarbazole（NVC） by using optically active anionic initiators such as the lithium salts of（S）-1-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-1-FIDH） and（S）-2-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-2-FIDH） and complexes of（-）-Sparteine with n-butylithium（n-Bu Li-（-）-Sp） or fluorenyl lithium（FILi-（-）-Sp） was achieved. The yield and specific rotation of poly（N-vinylcarbazole）s（poly（NVC）s） were considerably affected by the molar ratio of（S）-FIDH to NVC. The highest yield and specific rotation were obtained with Li-（S）-1-FIDH as an initiator, with a molar ratio of monomer and initiator [M]/[I] = 10/1. The effects of the chiral initiators, type of solvent and the polymerization temperature were investigated. The obtained optical activity of polymers was attributed to asymmetric induction of the chiral initiators.
文摘A simple synthesis of medicinally important cis-2-methyl-4-azapan-2-one-1,2,3,4-tetrahydroquinolines/cis-9- （2-methyl-l,2,3,4-tetrahydroquinolin-4-yl）-9H-carbazole was reported. Multicomponent one pot synthesis with ani- lines and N-vinylcaprolactam/N-vinyl carbazole via imino Diels-Alder reaction by using antimony trichloride as catalyst and acetonitrile as solvent was employed. NMR technique （2D） was used to study the regio- and stereo- chemistry of newly synthesized compounds. The cis diastereo-selectivity of the products was predicted by COSY and NOESY studies.
文摘The fluorescence spectra of the poly (N-vinylcarbazole) in solution obtained with chirally organic salts or acid as catalyst or initiator [ (-)Sp: (-)-Sparteine, (+)CSA: D- (+)Camphor-10-sulfonic acid)], respectively, have been investigated. It is found that the two emission peaks at the longer wavelength (lambda max, ca, 415nm) and the shorter wavelength (lambda max, ca, 370nm) are assigned to the sandwich excimer and second excimer (partial overlap) fluorescence, respectively. The sandwich excimer and partially overlapped excimer are attributed to a fully overlapped structure of neighbouring carbazole chromophores in a totally elipsed conformation of the isotactic sequence, and partially overlapped structure of the syndiotactic sequence. The estimated values of I-415/I-370 and isotactic sequence content by using the fluorescence spectra are in the order: (-)Sp(+) (+)CSA(-)> (+)CSA(-)> (-)Sp(+)ClO(4)(-) (no peak at 415nm for AIBN).
文摘The redox reaction between N-vinylcarbazole (NVC) and various oxidants including Ce(Ⅳ), Fe(Ⅲ)and benzoylperoxide in methanol proceeds via the initial formation of the NVC N-cation radical which in turn leads to the formation of the NVC cyclic dimer, trans-1,2-dicarbazylcyclobutane. Molecular oxygen and a few arylamines are able to accelerate the rate of the formation and increase the yield of the dimer. The mechanism of this process and the functions of oxygen and arylamines are presented as follows: The participation of molecular oxygen is to facilitate the dissociation of the resulting reduced metal ion and the NVC N-cation radical ion pair or charge transfer complex, thereby releasing the free NVC N-cation radical and increase the rate of the formation and yield of the dimer. The arylamine in this reaction between NVC and oxidants can be viewed as electron transfer agent between NVC and the oxidant. Because the amines are present in small amount relative to the oxidants and can be regenerated in process, it is essentially catalytic in nature.
文摘The organic salts as initiators [A*B-+(-):Ph*3C+ClO4-, Ph(3)*C+SbCl6-, (-)Sp*(ClO4-)-Cl-+ and (-)(Sp)(2)*(+3)(ClO4-)(3)] and catalysts [A(+)B*(-):(+)CSA*, A*B-+*(-):Ph(3)*C+(+)CSA*(-) and (-)Sp*(+)(+)CSA*] are prepared and characterized by specific rotation. The asymmetrically stereoselective induction of the initiators and catalysts in thc polymerization of N-vinylcarbazole is in an order of A*B-+*(-) > A(+)B*(-) > A*B-+(-). The specific rotations of obtained poly(N-vinylcarbazole) (PVCZ) generally are in accordance with mentioned order.
基金Supported by the China Postdoctoral Science Foundation under Grant No 2011M50070
文摘A kind of non-conjugated polymer memory material, poly（N-vinylcarbazole）, is used to investigate silicon-based storage performance with the fact that the one-bit storage cell circuit consists of a sandwiched indium-tin- oxide/poly（N-vinylcarbazole）/Al and an n-type metal-oxide-semiconductor field effect transistor. The memristor on the basis of a nano poly（N-vinylcarbazole） film exhibits electrical bistability and flash memory features, for which the switching-on voltage is -1 V and the on/off current ratio approaches 104. At ambient temperature, the memory circuit possesses higher reliability within the programming time 104 s. The output voltage is dose to 0.5 V during logic 1, while it is approximately 14mV in the logic 0. This paves the way for the study on the technology concerning the binary encoding and data storage of nonvolatile memories.
文摘A new PVK-based photorefractive polymer composite sensitized by C60 and doped with a higher content of EO chromophore was prepared. The high optical quality thin-film was formed between two ITOcovered glass electrodes. Two-beam-coupling (2BC) experiment was performed by using a He-Ne laser (at wavelength 632.8nm), and an obvious photorefractive performance was observed. The dependence of two-beamcoupling gain coefficient on the applied poling dc electric field was measured.
文摘Double-layer organic electroluminescent devices have been constructed. A new fluorescent dye, 9,10-bis(phenylethynyl)anthracence, was chosen as the dopant which was molecularly dispersed in the polymer film, and green light was observed from the device with luminance of 130cd/m(2) at 17V.
