以苯乙烯基三苯胺為電子給體模型化合物的合成與性能研究
發(fā)布時間：2018-08-12 19:51
【摘要】：在有機太陽能電池研究領域，發(fā)展新型有機光電功能材料以提高光電轉(zhuǎn)換效率和穩(wěn)定性能成為電池研究的一個重點方向，而三苯胺類衍生物因其高的摩爾消光系數(shù)，優(yōu)異的空穴遷移性能和強的給電子能力被廣泛應用于此類材料中。 本文合成一種4-苯乙烯基三苯胺結(jié)構(gòu)化合物（E）-1-苯基-2（4-N, N-二（甲基苯基）苯胺基）乙烯（MTPA），證實其能夠發(fā)生三苯胺到亞苯基的ICT作用。通過向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。系統(tǒng)性研究了給電子或吸電子取代基引入對MTPA基團ICT作用的影響，結(jié)果表明強吸電子基團（硝基或氰基取代丙烯酸）引入可以使得MTPA基團體現(xiàn)出高強度的、并影響單重激發(fā)態(tài)衰減途徑的ICT作用。 通過光誘導電子轉(zhuǎn)移生成長壽命電荷分離態(tài)有利于產(chǎn)生合適的光電流。本文將缺電子氮雜環(huán)化合物N取代二氯均三嗪（TRC）引入MTPA中，合成了一種新型Donor-Acceptor（D-A）有機半導體分子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），單重激發(fā)態(tài)1MTPA*-TRC向TRC基團發(fā)生電子轉(zhuǎn)移，所產(chǎn)生電荷分離態(tài)MTPA+.-TRC-.壽命為80ns。 接著按照階梯式能級設計思路，將第二受體氨基乙基氨基蒽醌（AEAQ）引入MTPA-TRC，構(gòu)建一種Donor-Acceptor1-Acceptor2（D-A1-A2）型雙極性有機半導體分子模型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）。單重激發(fā)態(tài)1MTPA*-TRC-AEAQ向TRC基團發(fā)生電子轉(zhuǎn)移，接著向AEAQ基團連續(xù)電子轉(zhuǎn)移；同時伴隨單重激發(fā)態(tài)MTPA-TRC-1AEAQ*向MTPA基團的空穴轉(zhuǎn)移。兩種轉(zhuǎn)移途徑所產(chǎn)生電荷分離態(tài)壽命MTPA.+-TRC-AEAQ.-約為650ns。 將無金屬四苯基卟啉基團（HTPP）引入MTPA-TRC，構(gòu)建一種D-A型雙極性半導體分子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），，其存在單重激發(fā)態(tài)MTPA基團向基態(tài)HTPP基團的空間電子轉(zhuǎn)移而不經(jīng)過TRC基團，同時伴隨單重激發(fā)態(tài)HTPP基團向基態(tài)MTPA基團的空穴轉(zhuǎn)移。但這兩種轉(zhuǎn)移途徑并未產(chǎn)生長壽命的電荷分離態(tài)（壽命小于10ns）。 利用強吸電子性的偶氮基團連接雙分子的4-苯乙烯基三苯胺，構(gòu)建了具有高強度ICT作用和高溶液電導率的模型化合物（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在甲磺酸中溶液電導率（0.01mol/L）高達106.7mS/cm。預示著MTPAAZO和TPAAZO在有機光電和導電材料領域可能存在一定的應用潛力。
[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.
【學位授予單位】：天津大學
【學位級別】：博士
【學位授予年份】：2014
【分類號】：O625.631;TM914.4
本文編號：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.
【學位授予單位】：天津大學
【學位級別】：博士
【學位授予年份】：2014
【分類號】：O625.631;TM914.4
【參考文獻】
相關期刊論文 前4條
1 宋文波,陳旭,吳芳,田文晶,馬淤光,許宏鼎;有機/聚合物材料體系能帶結(jié)構(gòu)的表征──電化學方法研究[J];高等學�；瘜W學報;2000年09期
2 任素貞;徐美玲;;離子液體基質(zhì)子交換膜的研究進展[J];電源技術;2014年02期
3 房喻,王輝;熒光壽命測定的現(xiàn)代方法與應用[J];化學通報;2001年10期
4 瞿三寅;花建麗;田禾;;新型D-π-A類敏化太陽電池染料及其應用[J];中國科學:化學;2012年05期
本文編號：2180176
本文鏈接：http://sikaile.net/kejilunwen/dianlilw/2180176.html
