线型齐聚噻吩衍生物的合成及其性能与应用研究
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摘要
齐聚噻吩作为一种有机功能材料,具有优异的光、电性能和良好的环境稳定性。为了研究和开发齐聚噻吩的新性能,开拓其在更广领域的应用,本文设计、合成了一系列齐聚噻吩及其衍生物。研究了它们的光、电性能,并在这个基础上,进一步研究了齐聚噻吩及其衍生物作为有机光致发光材料、有机光伏材料和有机电致变色材料的应用。
本论文中,所设计、合成的齐聚噻吩及其衍生物是:2,6-双(2,2′-二噻吩-5-基)吡啶(B2TPY)、5-醛基-2,2′-二噻吩(2T-CHO)、5,5′-双醛基-2,2′-二噻吩(2T-2CHO)、2,2′:5′,2″:5″,2″′-四噻吩(4T)、5,5″′-双氰基-2,2′:5′,2″:5″,2″′-四噻吩(4T-2CN)、5,5″′-双醛基-2,2′:5′,2″:5″,2″′-四噻吩(4T-2CHO)。并用质谱、核磁共振谱、红外光谱和高效液相色谱对目标化合物进行了确认表征。各齐聚噻吩及其衍生物的结构式如下:
测定了2T-CHO、2T-2CHO、4T、4T-2CHO、4T-2CN的紫外-可见光谱,利用荧光分光光度计对各个化合物的荧光量子效率进行了测定,测定了4T、4T-2CHO、4T-2CN的循环伏安曲线。
将B2TPY与稀土离子铽和铕配合,荧光分光光度计测试结果发现所得配合物均能发出各自中心稀土离子的特征荧光。
在对各化合物光电性能分析的基础上,以ITO玻璃和ITO柔性PET聚酯作为基底,分别用4T、4T-2CHO、4T-2CN作为电子给体材料,3,4,9,10-二萘嵌苯四甲酸二酐(PTCDA)作为电子受体材料,制备了刚性和柔性异质结光伏电池器件,对器件的光伏性能进行了研究。研究发现,以4T-2CN作为电子给体材料的刚性和柔性光伏器件具有较高的光电转换效率,分别为2.74%和1.94%。
对4T-2CHO的电致变色性能进行了研究,结果发现当进行电化学掺杂和去掺杂时,4T-2CHO膜的颜色可以发生由橙黄色变为赭色的可逆变化。
As a new kind of organic functional material, oligothiophene is getting more and more attention because of its excellent optoelectronic properties, anti-surroundings. In order to enlarge the application of this kind of material, a series of oligothiophene and its derivatives: 2,6-bis(2,2′-bithiophene-5-yl)pyridine(B2TPY), 5-formyl-2,2′-bithiophene(2T-CHO), 5,5′-bi- formyl-2,2′-bithiophene(2T-2CHO), 2,2′:5′,2″:5″,2″′-quaterthiophene(4T), 5,5″′-biformyl-2,2′: 5′,2″:5″,2″′-quaterthiophene (4T-2CHO) and 5,5″′-bicyano-2,2′:5′,2″:5″,2″′-quaterthiophene (4T-2CN) were designed and synthesized. Their molecular structures were charactered by MS, NMR, IR and HPLC.
The photophysical and electrochemical properties of these oligothiophene derivatives were measured by UV-vis absorption spectra, fluorescence spectra and cyclic voltammetry.
Complexes of B2TPY with rare-earth Terbium(Tb) and Europium(Eu) were prepared and charactered by IR, and their fluorescence spectras indicated that the energy transferation from the triplet state to single state was completed.
The photovoltaic performances of 4T, 4T-2CHO and 4T-2CN were investigated by the hard and flexible heterojunction organic photovoltaic devices. It was found that the best photoelectric conversion (PCE) efficiency of photovoltaic cells had reached 2.74% in the hard devices and 1.94% in the flexible devices.
The electrochromic property of 4T-2CHO was studied. The result showed the reversible color changes of the electrochemical doped film of 4T-2CHO was from orange to reddish brown. The result also suggested it had great potential as a new type of electrochromic material.
本论文中,所设计、合成的齐聚噻吩及其衍生物是:2,6-双(2,2′-二噻吩-5-基)吡啶(B2TPY)、5-醛基-2,2′-二噻吩(2T-CHO)、5,5′-双醛基-2,2′-二噻吩(2T-2CHO)、2,2′:5′,2″:5″,2″′-四噻吩(4T)、5,5″′-双氰基-2,2′:5′,2″:5″,2″′-四噻吩(4T-2CN)、5,5″′-双醛基-2,2′:5′,2″:5″,2″′-四噻吩(4T-2CHO)。并用质谱、核磁共振谱、红外光谱和高效液相色谱对目标化合物进行了确认表征。各齐聚噻吩及其衍生物的结构式如下:
测定了2T-CHO、2T-2CHO、4T、4T-2CHO、4T-2CN的紫外-可见光谱,利用荧光分光光度计对各个化合物的荧光量子效率进行了测定,测定了4T、4T-2CHO、4T-2CN的循环伏安曲线。
将B2TPY与稀土离子铽和铕配合,荧光分光光度计测试结果发现所得配合物均能发出各自中心稀土离子的特征荧光。
在对各化合物光电性能分析的基础上,以ITO玻璃和ITO柔性PET聚酯作为基底,分别用4T、4T-2CHO、4T-2CN作为电子给体材料,3,4,9,10-二萘嵌苯四甲酸二酐(PTCDA)作为电子受体材料,制备了刚性和柔性异质结光伏电池器件,对器件的光伏性能进行了研究。研究发现,以4T-2CN作为电子给体材料的刚性和柔性光伏器件具有较高的光电转换效率,分别为2.74%和1.94%。
对4T-2CHO的电致变色性能进行了研究,结果发现当进行电化学掺杂和去掺杂时,4T-2CHO膜的颜色可以发生由橙黄色变为赭色的可逆变化。
As a new kind of organic functional material, oligothiophene is getting more and more attention because of its excellent optoelectronic properties, anti-surroundings. In order to enlarge the application of this kind of material, a series of oligothiophene and its derivatives: 2,6-bis(2,2′-bithiophene-5-yl)pyridine(B2TPY), 5-formyl-2,2′-bithiophene(2T-CHO), 5,5′-bi- formyl-2,2′-bithiophene(2T-2CHO), 2,2′:5′,2″:5″,2″′-quaterthiophene(4T), 5,5″′-biformyl-2,2′: 5′,2″:5″,2″′-quaterthiophene (4T-2CHO) and 5,5″′-bicyano-2,2′:5′,2″:5″,2″′-quaterthiophene (4T-2CN) were designed and synthesized. Their molecular structures were charactered by MS, NMR, IR and HPLC.
The photophysical and electrochemical properties of these oligothiophene derivatives were measured by UV-vis absorption spectra, fluorescence spectra and cyclic voltammetry.
Complexes of B2TPY with rare-earth Terbium(Tb) and Europium(Eu) were prepared and charactered by IR, and their fluorescence spectras indicated that the energy transferation from the triplet state to single state was completed.
The photovoltaic performances of 4T, 4T-2CHO and 4T-2CN were investigated by the hard and flexible heterojunction organic photovoltaic devices. It was found that the best photoelectric conversion (PCE) efficiency of photovoltaic cells had reached 2.74% in the hard devices and 1.94% in the flexible devices.
The electrochromic property of 4T-2CHO was studied. The result showed the reversible color changes of the electrochemical doped film of 4T-2CHO was from orange to reddish brown. The result also suggested it had great potential as a new type of electrochromic material.
引文
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