以苯乙烯基三苯胺为电子给体模型化合物的合成与性能研究
发布时间：2018-08-12 19:51
【摘要】：在有机太阳能电池研究领域，发展新型有机光电功能材料以提高光电转换效率和稳定性能成为电池研究的一个重点方向，而三苯胺类衍生物因其高的摩尔消光系数，优异的空穴迁移性能和强的给电子能力被广泛应用于此类材料中。 本文合成一种4-苯乙烯基三苯胺结构化合物（E）-1-苯基-2（4-N, N-二（甲基苯基）苯胺基）乙烯（MTPA），证实其能够发生三苯胺到亚苯基的ICT作用。通过向MTPA上引入氨基、甲氧基、氯基、氰基、硝基和氰基取代丙烯酸，合成了系列化合物。系统性研究了给电子或吸电子取代基引入对MTPA基团ICT作用的影响，结果表明强吸电子基团（硝基或氰基取代丙烯酸）引入可以使得MTPA基团体现出高强度的、并影响单重激发态衰减途径的ICT作用。 通过光诱导电子转移生成长寿命电荷分离态有利于产生合适的光电流。本文将缺电子氮杂环化合物N取代二氯均三嗪（TRC）引入MTPA中，合成了一种新型Donor-Acceptor（D-A）有机半导体分子1-（4-（3,5-二氯三嗪）氨基苯基）-2（4-N,N-二（甲基苯基）苯胺基）乙烯（MTPA-TRC），单重激发态1MTPA*-TRC向TRC基团发生电子转移，所产生电荷分离态MTPA+.-TRC-.寿命为80ns。 接着按照阶梯式能级设计思路，将第二受体氨基乙基氨基蒽醌（AEAQ）引入MTPA-TRC，构建一种Donor-Acceptor1-Acceptor2（D-A1-A2）型双极性有机半导体分子模型4,4-二甲基-4-(4-(4-氯-6-(2-(9,10-二氧蒽-1-氨基)乙基氨基)-1,3,5-三嗪-2-氨基)苯乙烯基)三苯基胺（MTPA-TRC-AEAQ）。单重激发态1MTPA*-TRC-AEAQ向TRC基团发生电子转移，接着向AEAQ基团连续电子转移；同时伴随单重激发态MTPA-TRC-1AEAQ*向MTPA基团的空穴转移。两种转移途径所产生电荷分离态寿命MTPA.+-TRC-AEAQ.-约为650ns。 将无金属四苯基卟啉基团（HTPP）引入MTPA-TRC，构建一种D-A型双极性半导体分子4,4-二甲基-4-(4-(4-氯-6-(4-(10,15,20-三苯基卟啉)苯基)氨基-1,3,5-三嗪-2-氨基)苯乙烯基)三苯基胺（MTPAt-HTPP），，其存在单重激发态MTPA基团向基态HTPP基团的空间电子转移而不经过TRC基团，同时伴随单重激发态HTPP基团向基态MTPA基团的空穴转移。但这两种转移途径并未产生长寿命的电荷分离态（寿命小于10ns）。 利用强吸电子性的偶氮基团连接双分子的4-苯乙烯基三苯胺，构建了具有高强度ICT作用和高溶液电导率的模型化合物（E）-二（4-（4-（N，N’-二甲基苯基）氨基-苯基乙烯基）苯基）氮烯（MTPAAZO）和（E）-二（4-（4-（N, N’-二苯基）氨基-苯基乙烯基）苯基）氮烯（TPAAZO），其中MTPAAZO在甲磺酸中溶液电导率（0.01mol/L）高达106.7mS/cm。预示着MTPAAZO和TPAAZO在有机光电和导电材料领域可能存在一定的应用潜力。
[Abstract]:In the research field of organic solar cells, the development of novel organic photovoltaic functional materials to improve photoelectric conversion efficiency and stability has become an important research direction of the battery, while the triphenylamine derivatives have high molar extinction coefficient. Excellent hole migration performance and strong electron-donating ability are widely used in this kind of materials. In this paper, a 4-styrene-trianiline structure compound (E) -1-phenyl -2 (4-N, N-bis (methyl phenyl) aniline) ethylene (MTPA), has been synthesized. It has been proved that it can produce the ICT interaction between trianiline and phenyl. A series of compounds were synthesized by introducing amino, methoxy, chloro, cyanyl, nitro and cyano-substituted acrylic acid into MTPA. The effect of the introduction of electron or electron absorbing substituents on the action of MTPA group ICT is systematically studied. The results show that the introduction of strong electron absorbing groups (nitro or cyanoacrylic acid) can make the MTPA groups exhibit high strength. The ICT effect of the single excited state attenuation pathway is also affected. The charge separation state generated by photo-induced electron transfer is conducive to the generation of appropriate photocurrent. In this paper, electron-deficient nitrogen-deficient heterocyclic compound N-substituted dichlorotriazine (TRC) was introduced into MTPA. A novel Donor-Acceptor (D-A) organic semiconductor molecule 1- (4- (3- (3- (3-) -dichlorotriazine) aminophenyl) -2 (4-N- (N-bis (methyl phenyl) aniline) ethylene (MTPA-TRC) was synthesized. The single excited state of 1MTPA*-TRC was transferred to the TRC group, resulting in the charge separation state MTPA .-TRC-. The life span is 80 ns. Then according to the step energy level design idea, The second receptor aminoethyl aminoanthraquinone (AEAQ) was introduced into MTPA-TRC to construct a Donor-Acceptor1-Acceptor2 (D-A1-A2) bipolar organic semiconductor molecular model of 4- (4- (4- (9- (9- (9-) -dioxanthracene-1-amino) ethylanthraquinone) -1- (35-triazine-2-amino) styrene-triphenylamine (MTPA-TRC-AEAQ). The single excited state 1MTPA*-TRC-AEAQ transports to the TRC group, then to the AEAQ group, and the hole transfer to the MTPA group accompanied by the single excited state MTPA-TRC-1AEAQ *. The lifetime of charge separation state produced by the two transfer pathways is about 650 ns.-TRC-AEAQ. In this paper, a D-A bipolar semiconductor molecule 4- 4- dimethyl-4- (4- (4- (4- (1015155- triphenylporphyrin) phenyl) amino-1- (3- triazine-2-amino) styrene) triphenylamine (MTPAt-HTPP) was synthesized by introducing the metal-free tetraphenylporphyrin group (HTPP) into MTPA-TRC.The dimethyl-4- (4- (4- (4- (4-) -chloro-20-triphenylporphyrin) phenyl) amino group (MTPAt-HTPP) was synthesized. The spatial electron transfer from the generated MTPA group to the ground state HTPP group does not pass through the TRC group. At the same time, the hole transfer from HTPP group to ground state MTPA group is accompanied by single excited state. However, these two transfer pathways do not produce a long lifetime charge separation state (the lifetime is less than 10ns). A strong electron-absorbent azo group was used to connect bimolecular 4-styrene-trianiline. A model compound (E)-bis (4- (4- (4- (4- (4- (N- (N- (N- (N- (N-) N- (N-, N-, N-) diphenyl) amino-phenyl) (MTPAAZO) and (E)-bis (4- (4- (4- (N-, N-, N-) -diphenylamino) -phenyl vinyl) was constructed with high intensity of ICT action and high conductivity of solution. Phenyl) azene (TPAAZO), in which the conductivity (0.01mol/L) of MTPAAZO in mesonic acid solution was 106.7 Ms / cm ~ (-1). It indicates that MTPAAZO and TPAAZO may have some potential applications in the field of organic optoelectronic and conductive materials.
【学位授予单位】：天津大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：O625.631;TM914.4
本文编号：2180176
[Abstract]:In the research field of organic solar cells, the development of novel organic photovoltaic functional materials to improve photoelectric conversion efficiency and stability has become an important research direction of the battery, while the triphenylamine derivatives have high molar extinction coefficient. Excellent hole migration performance and strong electron-donating ability are widely used in this kind of materials. In this paper, a 4-styrene-trianiline structure compound (E) -1-phenyl -2 (4-N, N-bis (methyl phenyl) aniline) ethylene (MTPA), has been synthesized. It has been proved that it can produce the ICT interaction between trianiline and phenyl. A series of compounds were synthesized by introducing amino, methoxy, chloro, cyanyl, nitro and cyano-substituted acrylic acid into MTPA. The effect of the introduction of electron or electron absorbing substituents on the action of MTPA group ICT is systematically studied. The results show that the introduction of strong electron absorbing groups (nitro or cyanoacrylic acid) can make the MTPA groups exhibit high strength. The ICT effect of the single excited state attenuation pathway is also affected. The charge separation state generated by photo-induced electron transfer is conducive to the generation of appropriate photocurrent. In this paper, electron-deficient nitrogen-deficient heterocyclic compound N-substituted dichlorotriazine (TRC) was introduced into MTPA. A novel Donor-Acceptor (D-A) organic semiconductor molecule 1- (4- (3- (3- (3-) -dichlorotriazine) aminophenyl) -2 (4-N- (N-bis (methyl phenyl) aniline) ethylene (MTPA-TRC) was synthesized. The single excited state of 1MTPA*-TRC was transferred to the TRC group, resulting in the charge separation state MTPA .-TRC-. The life span is 80 ns. Then according to the step energy level design idea, The second receptor aminoethyl aminoanthraquinone (AEAQ) was introduced into MTPA-TRC to construct a Donor-Acceptor1-Acceptor2 (D-A1-A2) bipolar organic semiconductor molecular model of 4- (4- (4- (9- (9- (9-) -dioxanthracene-1-amino) ethylanthraquinone) -1- (35-triazine-2-amino) styrene-triphenylamine (MTPA-TRC-AEAQ). The single excited state 1MTPA*-TRC-AEAQ transports to the TRC group, then to the AEAQ group, and the hole transfer to the MTPA group accompanied by the single excited state MTPA-TRC-1AEAQ *. The lifetime of charge separation state produced by the two transfer pathways is about 650 ns.-TRC-AEAQ. In this paper, a D-A bipolar semiconductor molecule 4- 4- dimethyl-4- (4- (4- (4- (1015155- triphenylporphyrin) phenyl) amino-1- (3- triazine-2-amino) styrene) triphenylamine (MTPAt-HTPP) was synthesized by introducing the metal-free tetraphenylporphyrin group (HTPP) into MTPA-TRC.The dimethyl-4- (4- (4- (4- (4-) -chloro-20-triphenylporphyrin) phenyl) amino group (MTPAt-HTPP) was synthesized. The spatial electron transfer from the generated MTPA group to the ground state HTPP group does not pass through the TRC group. At the same time, the hole transfer from HTPP group to ground state MTPA group is accompanied by single excited state. However, these two transfer pathways do not produce a long lifetime charge separation state (the lifetime is less than 10ns). A strong electron-absorbent azo group was used to connect bimolecular 4-styrene-trianiline. A model compound (E)-bis (4- (4- (4- (4- (4- (N- (N- (N- (N- (N-) N- (N-, N-, N-) diphenyl) amino-phenyl) (MTPAAZO) and (E)-bis (4- (4- (4- (N-, N-, N-) -diphenylamino) -phenyl vinyl) was constructed with high intensity of ICT action and high conductivity of solution. Phenyl) azene (TPAAZO), in which the conductivity (0.01mol/L) of MTPAAZO in mesonic acid solution was 106.7 Ms / cm ~ (-1). It indicates that MTPAAZO and TPAAZO may have some potential applications in the field of organic optoelectronic and conductive materials.
【学位授予单位】：天津大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：O625.631;TM914.4
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