Synthesis of conductive polymer poly([thiophene]-[benzo[1,2,3]thiadiazole] [thiophene]) (abbreviated as P(T-Btdaz-T)) was achieved by electrochemical polymerization in hydroxypropyl cellulose (HPC)/N,N-dimethylformami...Synthesis of conductive polymer poly([thiophene]-[benzo[1,2,3]thiadiazole] [thiophene]) (abbreviated as P(T-Btdaz-T)) was achieved by electrochemical polymerization in hydroxypropyl cellulose (HPC)/N,N-dimethylformamide (DMF) in liquid crystal state. The polymer thus obtained shows fingerprint texture, which is derived from helical structure of the HPC in cholesteric liquid crystal state. Fourier transform infrared spectroscopy measurements revealed that the polymer film is P(T-Btdaz-T)/HPC composite. Circular dichroism optical absorption spectroscopy measurements show that the polymer has the optical activity. Next, electrochemical polymerization of 3,4-ethylene-dioxythiophene (EDOT) was carried out in columnar phase liquid crystal. The polymer transcribes the columnar structure and shows optical structure resembling columnar liquid crystal electrolyte solution.展开更多
The phase behaviors and structures of a triphenylene-derived discotic liquid crystal （LC） hexa-n-octoxyl- triphenylene （C8HET） were studied using the combined techniques of differential scanning calorimetry （DSC...The phase behaviors and structures of a triphenylene-derived discotic liquid crystal （LC） hexa-n-octoxyl- triphenylene （C8HET） were studied using the combined techniques of differential scanning calorimetry （DSC）, wide angle X-ray diffraction （WAXD）, selected area electron diffraction （SAED） and polarized light microscopy （PLM）. Onedimensional （1D） powder WAXD results at different temperatures coupled with DSC and PLM observations revealed that the C8HET compound possessed an LC phase and three different crystalline （K3, K2 and K1） phases below the isotropic （I） melt. The I←→ LC phase transition was thermodynamically reversible and independent of the heating and cooling rates. The development and experimental observation of the three crystalline phases relied on different thermal histories. Among the three crystalline phases in CSHET, the K3 phase is the most stable phase, while the K2 and K1 phases are metastable. Note that the K1 phase only formed via a quenching process. Oh the basis of structure sensitive diffraction experiments such as 2D WAXD of oriented samples and SAED of single crystals, detailed structures and molecular packings of these four ordered phases were identified. The LC phase exhibited a hexagonal columnar phase with 2D lattice dimensions ofa = b = 2.38 nm and γ= 120°. All the three crystalline phases possess monoclinic unit cells, yet the y angle is not 90° in the cases of the K2 and the K3 phases, while in the case of the K1 phase the a angle is not 90°.展开更多
Small change in chemical structure of discotic liquid crystals can cause big difference in their mesomorphism. Replacing of the alkoxy peripheral chains of triphenylene by oxygen-atom containing ester chains would res...Small change in chemical structure of discotic liquid crystals can cause big difference in their mesomorphism. Replacing of the alkoxy peripheral chains of triphenylene by oxygen-atom containing ester chains would result in novel mesomorphism. A series of mixed tail triphenylenes containing propoxyacetyloxy and alkoxy, abbreviated as C18H6（OCnH2n＋1）3（OCOCH2OC3H7）3, n=4-8, and hexa（propyloxyacetyloxy）triphenylene, C18H6（OCOCH2OC3H7）6 were synthesized. Thermal gravimetry analysis （TGA） of three discogens showed that they had good thermal stability till 350 ℃. The mesomorphism was investigated through differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The preliminary X-ray diffraction （XRD） results of one compound showed that it exhibited ordered hexagonal columnar （Colho） mesophase. These mixed tail triphenylene derivatives possessed much stable Colho mesophase and wider mesophase ranges than their hexaalkoxytriphenylene C18H6（OR）6 and hexaalkanoyloxytriphenylene C18H6（OCOR＇）6 analogues. The asymmetrical compounds 2,6,11-trialkoxy-3,7,10-tri（2-propyloxyacetyloxy）triphenylenes with n=5-8 displayed higher clearing points and wider temperature ranges than their symmetrical isomers 2,6,10-trialkoxy-3,7,11-tri（2-propyloxyacetyloxy）- triphenylenes, while C18H6（OCOCH2OC3H7）6 had the highest clearing point due to the β-oxygen-atom effect.展开更多
Connecting two discotic mesogens via a spacer not only stabilizes the columnar mesophase but also leads to the formation of glass columnar phase, and therefore improves the physical properties of discotic liquid cryst...Connecting two discotic mesogens via a spacer not only stabilizes the columnar mesophase but also leads to the formation of glass columnar phase, and therefore improves the physical properties of discotic liquid crystals as organic semiconductor. Here, we report the synthesis of eight diacetylene-bridged triphenylene discotic liquid crystal dimers, [C18H6(OC n H2n+1)4(OMe)O2C?C8H16?C≡C?]2, 3(n), (n = 4–8), [C18H6(OC6H13)5O2C?C8H16?C≡C?]2, 6 and [C18H6(OC6H13)5O?(CH2)m?C≡C?]2, 8(m), (m = 1, 3) by Eglinton coupling reaction. The thermotropic liquid crystal properties were studied by differential scanning calorimetry and polarized optical microscopy. The results are showed as follows: the length of peripheral alkyl chains of triphenylene influenced properties of liquid crystal dimers; dimers 3(n) (n = 5–8) and 6 had glass columnar phase, and no crystallization was observed above ?50°C for all the triphenylene dimers; compared with 3(6), 6 showed higher molecular symmetry, more stable columnar mesophase and wider mesophase range. The connecting group, length and rigidity of spacer had important influence on the mesomorphism of diacetylene-bridged triphenylene discotic liquid crystal dimers.展开更多
Two bowlic cyclotriveratrylene CTV-1 and CTV-2, with different peripheral groups of -OCH3 and -OCH2CH3 for CTV-1 and -OCH3 and -OCH2COOCH3 for CTV-2, respectively, were synthesized by typical trimerization via a multi...Two bowlic cyclotriveratrylene CTV-1 and CTV-2, with different peripheral groups of -OCH3 and -OCH2CH3 for CTV-1 and -OCH3 and -OCH2COOCH3 for CTV-2, respectively, were synthesized by typical trimerization via a multistep sequence from vanillin. Both bowlic CTV molecules were thermotropic liquid crystals, and presented typical grainy textures of the nematic phase and homogeneous texture of the single domain nematic phase. It is of interest to observe the regular and beautiful mosaic-like morphologies after cooling from liquid crystalline phases, which appeared and vanished repeatedly in several circles of cooling and heating. The size of each mosaic was several dozens of micron. In nature, the mosaic-like morphologies are the optical pattern of cracks formed by the shrinking, due to the crystallization of frozen texture of nematic phases. By means of scanning electron microscopy, the mosaic-like morphologies were observed to consist of lamellae, and each mosaic is a rectangular multi-layer lamella, which is composed of packed single-layered lamellae. The fibrils in the diameter of about 1 μm were observed, which are the structural units of lamellae and would be the bundles of the bowlic molecular columns. The mosaic-like morphologies decorate the bowlic molecular columnar nematic phase, therefore, a novel mosaic-like morphologies decoration method was applied to reveal the director distribution of several kinds of point disclinations, such as s = +1(δ =0°and δ =90°) and s = ±1/2, and Nèel domain walls. It was shown that the bowlic molecular columnar nematic phase behaved as normal nematic phases; however, the basic structural units ordered were the bowlic molecular column or the bundles of bowlic molecular column (i.e. fibrils), but not the bowlic molecules themselves. The bowlic molecular columns acted as the rod-like molecules in a normal nematic phase. Therefore, a new term BCN (bowlic columnar nematic phase) is used to describe the anomalous nematic phase in this paper.展开更多
Novel bent shape tenary facial amphiphilic imidazolium ILC which consist of a ^-conjugated bent aromatic cores （2,5-dithiophenylethynyl phenyl bent core）, two terminal poliphilic alkyl chains and lateral n-alky chai...Novel bent shape tenary facial amphiphilic imidazolium ILC which consist of a ^-conjugated bent aromatic cores （2,5-dithiophenylethynyl phenyl bent core）, two terminal poliphilic alkyl chains and lateral n-alky chain terminated by an imidazolium bromide unit were synthesized by using Kumada and Sonogashira coupling reactions as key steps and both their thermotropic and lyotropic mesophase behaviors were studied by POM, DSC and XRD. Columnar phases were found in these compounds, a hexagonal cylinder model with core shell structure is supposed for the columnar phase formed by compound 1/8. Our study may provide a new strategy for designing new LC functional material.展开更多
文摘Synthesis of conductive polymer poly([thiophene]-[benzo[1,2,3]thiadiazole] [thiophene]) (abbreviated as P(T-Btdaz-T)) was achieved by electrochemical polymerization in hydroxypropyl cellulose (HPC)/N,N-dimethylformamide (DMF) in liquid crystal state. The polymer thus obtained shows fingerprint texture, which is derived from helical structure of the HPC in cholesteric liquid crystal state. Fourier transform infrared spectroscopy measurements revealed that the polymer film is P(T-Btdaz-T)/HPC composite. Circular dichroism optical absorption spectroscopy measurements show that the polymer has the optical activity. Next, electrochemical polymerization of 3,4-ethylene-dioxythiophene (EDOT) was carried out in columnar phase liquid crystal. The polymer transcribes the columnar structure and shows optical structure resembling columnar liquid crystal electrolyte solution.
基金This work was supported by National Science Foundation of USA (DMR-0516602). The 1D X-ray diffraction research was carried out at the National Synchrotron Light Source in Brookhaven National Laboratory supported by the Department of Energy.
文摘The phase behaviors and structures of a triphenylene-derived discotic liquid crystal （LC） hexa-n-octoxyl- triphenylene （C8HET） were studied using the combined techniques of differential scanning calorimetry （DSC）, wide angle X-ray diffraction （WAXD）, selected area electron diffraction （SAED） and polarized light microscopy （PLM）. Onedimensional （1D） powder WAXD results at different temperatures coupled with DSC and PLM observations revealed that the C8HET compound possessed an LC phase and three different crystalline （K3, K2 and K1） phases below the isotropic （I） melt. The I←→ LC phase transition was thermodynamically reversible and independent of the heating and cooling rates. The development and experimental observation of the three crystalline phases relied on different thermal histories. Among the three crystalline phases in CSHET, the K3 phase is the most stable phase, while the K2 and K1 phases are metastable. Note that the K1 phase only formed via a quenching process. Oh the basis of structure sensitive diffraction experiments such as 2D WAXD of oriented samples and SAED of single crystals, detailed structures and molecular packings of these four ordered phases were identified. The LC phase exhibited a hexagonal columnar phase with 2D lattice dimensions ofa = b = 2.38 nm and γ= 120°. All the three crystalline phases possess monoclinic unit cells, yet the y angle is not 90° in the cases of the K2 and the K3 phases, while in the case of the K1 phase the a angle is not 90°.
基金Project supported by the National Natural Science Foundation of China （Nos. 50473062, 50673069）, the Sichuan Province Youth Foundation （No. 04-ZQ026-044） and the Research Project of Sichuan Province （No. 05GG009-005）, China.
文摘Small change in chemical structure of discotic liquid crystals can cause big difference in their mesomorphism. Replacing of the alkoxy peripheral chains of triphenylene by oxygen-atom containing ester chains would result in novel mesomorphism. A series of mixed tail triphenylenes containing propoxyacetyloxy and alkoxy, abbreviated as C18H6（OCnH2n＋1）3（OCOCH2OC3H7）3, n=4-8, and hexa（propyloxyacetyloxy）triphenylene, C18H6（OCOCH2OC3H7）6 were synthesized. Thermal gravimetry analysis （TGA） of three discogens showed that they had good thermal stability till 350 ℃. The mesomorphism was investigated through differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The preliminary X-ray diffraction （XRD） results of one compound showed that it exhibited ordered hexagonal columnar （Colho） mesophase. These mixed tail triphenylene derivatives possessed much stable Colho mesophase and wider mesophase ranges than their hexaalkoxytriphenylene C18H6（OR）6 and hexaalkanoyloxytriphenylene C18H6（OCOR＇）6 analogues. The asymmetrical compounds 2,6,11-trialkoxy-3,7,10-tri（2-propyloxyacetyloxy）triphenylenes with n=5-8 displayed higher clearing points and wider temperature ranges than their symmetrical isomers 2,6,10-trialkoxy-3,7,11-tri（2-propyloxyacetyloxy）- triphenylenes, while C18H6（OCOCH2OC3H7）6 had the highest clearing point due to the β-oxygen-atom effect.
基金Supported by the National Natural Science Foundation of China(Grant Nos.50473062,50673069,and 50811140156)
文摘Connecting two discotic mesogens via a spacer not only stabilizes the columnar mesophase but also leads to the formation of glass columnar phase, and therefore improves the physical properties of discotic liquid crystals as organic semiconductor. Here, we report the synthesis of eight diacetylene-bridged triphenylene discotic liquid crystal dimers, [C18H6(OC n H2n+1)4(OMe)O2C?C8H16?C≡C?]2, 3(n), (n = 4–8), [C18H6(OC6H13)5O2C?C8H16?C≡C?]2, 6 and [C18H6(OC6H13)5O?(CH2)m?C≡C?]2, 8(m), (m = 1, 3) by Eglinton coupling reaction. The thermotropic liquid crystal properties were studied by differential scanning calorimetry and polarized optical microscopy. The results are showed as follows: the length of peripheral alkyl chains of triphenylene influenced properties of liquid crystal dimers; dimers 3(n) (n = 5–8) and 6 had glass columnar phase, and no crystallization was observed above ?50°C for all the triphenylene dimers; compared with 3(6), 6 showed higher molecular symmetry, more stable columnar mesophase and wider mesophase range. The connecting group, length and rigidity of spacer had important influence on the mesomorphism of diacetylene-bridged triphenylene discotic liquid crystal dimers.
基金Supported by the National Natural Science Foundation of China (Grant No. 20774077)the Natural Science Foundation of Fujian, China (Grant Nos. E0510003 & E0710025)the Project of Science and Technology of Xiamen, China (Grant No. 3502Z20055013)
文摘Two bowlic cyclotriveratrylene CTV-1 and CTV-2, with different peripheral groups of -OCH3 and -OCH2CH3 for CTV-1 and -OCH3 and -OCH2COOCH3 for CTV-2, respectively, were synthesized by typical trimerization via a multistep sequence from vanillin. Both bowlic CTV molecules were thermotropic liquid crystals, and presented typical grainy textures of the nematic phase and homogeneous texture of the single domain nematic phase. It is of interest to observe the regular and beautiful mosaic-like morphologies after cooling from liquid crystalline phases, which appeared and vanished repeatedly in several circles of cooling and heating. The size of each mosaic was several dozens of micron. In nature, the mosaic-like morphologies are the optical pattern of cracks formed by the shrinking, due to the crystallization of frozen texture of nematic phases. By means of scanning electron microscopy, the mosaic-like morphologies were observed to consist of lamellae, and each mosaic is a rectangular multi-layer lamella, which is composed of packed single-layered lamellae. The fibrils in the diameter of about 1 μm were observed, which are the structural units of lamellae and would be the bundles of the bowlic molecular columns. The mosaic-like morphologies decorate the bowlic molecular columnar nematic phase, therefore, a novel mosaic-like morphologies decoration method was applied to reveal the director distribution of several kinds of point disclinations, such as s = +1(δ =0°and δ =90°) and s = ±1/2, and Nèel domain walls. It was shown that the bowlic molecular columnar nematic phase behaved as normal nematic phases; however, the basic structural units ordered were the bowlic molecular column or the bundles of bowlic molecular column (i.e. fibrils), but not the bowlic molecules themselves. The bowlic molecular columns acted as the rod-like molecules in a normal nematic phase. Therefore, a new term BCN (bowlic columnar nematic phase) is used to describe the anomalous nematic phase in this paper.
基金the National Natural Science Foundation of China，the Yunnan Science Foundation
文摘Novel bent shape tenary facial amphiphilic imidazolium ILC which consist of a ^-conjugated bent aromatic cores （2,5-dithiophenylethynyl phenyl bent core）, two terminal poliphilic alkyl chains and lateral n-alky chain terminated by an imidazolium bromide unit were synthesized by using Kumada and Sonogashira coupling reactions as key steps and both their thermotropic and lyotropic mesophase behaviors were studied by POM, DSC and XRD. Columnar phases were found in these compounds, a hexagonal cylinder model with core shell structure is supposed for the columnar phase formed by compound 1/8. Our study may provide a new strategy for designing new LC functional material.
