含三苯胺结构的非对称型苝酰亚胺的合成及性能

doi:10.7503/cjcu20150549

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (12): 2409.doi: 10.7503/cjcu20150549

含三苯胺结构的非对称型苝酰亚胺的合成及性能

孔鲁诗¹, 田国峰¹, 李丰¹, 齐胜利^1,²(), 武德珍^1,²

1. 北京化工大学化工资源有效利用国家重点实验室, 北京 100029
2. 北京化工大学常州先进材料研究院, 常州 213164

收稿日期:2015-07-14 出版日期:2015-12-10 发布日期:2015-11-17
作者简介:联系人简介: 齐胜利, 男, 博士, 教授, 博士生导师, 主要从事高性能聚合物研究. E-mail:qisl@mail.buct.edu.cn
基金资助:
国家自然科学基金(批准号: 50903006)、中央高校科研业务费项目基金(批准号: ZZ1306)和江苏省自然科学基金(批准号: BK20130256, BK20140006)资助

Synthesis and Properties of Triphenylamine-containing Asymmetrical Perylene Diimides^†

KONG Lushi¹, TIAN Guofeng¹, LI Feng¹, QI Shengli^1,^2,^*(), WU Dezhen^1,²

1. State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology, Beijing 100029, China
2. Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164, China

Received:2015-07-14 Online:2015-12-10 Published:2015-11-17
Contact: QI Shengli E-mail:qisl@mail.buct.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.050903006), the Fundamental Research Funds for the Central Universities of China(No.ZZ1306) and the Natural Science Foundation of Jiangsu Province, China(Nos.BK20130256, BK20140006)

摘要/Abstract

摘要：

合成了2种含有三苯胺结构的非对称型苝酰亚胺N-(2-乙基己基)-N'-(4-三苯胺)-3,4,9,10-苝二酰亚胺(PDI-ATPA)和4,4',4″-三[N-(2-乙基己基)-3,4,9,10-苝二酰亚胺]-三苯胺(PDI-TATPA). 利用核磁共振谱(NMR)、红外光谱(IR)和元素分析等方法表征了2种分子的结构, 采用紫外-可见(UV-Vis)吸收光谱和荧光光谱研究了其分子光物理性能及在溶液中的聚集行为, 并且对分子轨道、能级和偶极矩进行了分子模拟. 研究结果表明, 具有星形空间对称结构的苝酰亚胺分子PDI-TATPA在溶液中具有自组装行为; 引入的三苯胺结构与苝核形成电子给体-受体结构, 发生分子内电子转移(PET), 进而导致荧光猝灭.

关键词: 三苯胺, 苝酰亚胺, 非对称, 自组装

Abstract:

Two asymmetrical perylene diimides with triphenylamine structure, N-(2-ethylhexyl)-N'-(4-triphenylamine)-3, 4, 9, 10-perylene diimide(PDI-ATPA) and 4, 4', 4''-tri[N-(2-ethylhexyl)-3, 4, 9, 10-perylene diimide]-triphenylamine(PDI-TATPA), were designed and synthesized, using branched alkyl chain substituted asymmetrical perylene monoanhydride monoimide(AsPDA-Ⅰ) as the electron-accepting species and different functional triphenylamines, 4-aminotriphenylamine(ATPA) and 4, 4', 4''-triaminotriphenylamine(TATPA), as the electron-donating moieties, respectively. The chemical structures were characterized by proton nuclear magnetic resonance(¹H NMR), Infrared(IR) spectra and elemental analysis. The optical properties and aggregation behavior in solution were investigated by UV-Vis absorption and fluorescence emission spectra. Besides, molecular simulations were carried out to elucidate the molecular orbitals, energy levels and dipole moments of two asymmetrical perylene diimides. The results demonstrated that introducing the triphenylamine structure at the imide nitrogen of perylene diimide not only broadens the photo absorption region of perylene diimide but also has no effect on the absorption properties of the perylene core because of nodes in the highes occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) at the imide nitrogen. Photoinduced electron transfer(PET) process take place from the eletron-donating moieties-ATPA and TATPA to the electron-accepting unit-perylene core, which has been confirmed by molecular simulations and lead to the fluorescence quenching. PDI-TATPA showed a star-shaped structure with highly regularity, which has been proven by the simulation data of dipole moment and has caused the self-assembly behavior easily occur in solution. Due to the self-assembly behavior, there are some differences between the UV-Vis spectra of PDI-ATPA and that of PDI-TATPA.

Key words: Triphenylamine, Perylene diimide, Asymmetrical, Self-assembly

中图分类号:

O621.1

TrendMD:

孔鲁诗, 田国峰, 李丰, 齐胜利, 武德珍. 含三苯胺结构的非对称型苝酰亚胺的合成及性能. 高等学校化学学报, 2015, 36(12): 2409.

KONG Lushi, TIAN Guofeng, LI Feng, QI Shengli, WU Dezhen. Synthesis and Properties of Triphenylamine-containing Asymmetrical Perylene Diimides^†. Chem. J. Chinese Universities, 2015, 36(12): 2409.

图/表 8

Table 1 Elemental analysis, UV-Vis, and IR data of PDI-ATPA and PDI-TATPA

Compd.		Elemental analysis(%, calcd.)					UV-Vis(CHCl₃), λ_max/nm	IR(KBr), $ν ˙$ /cm^-1
Compd.		C		H		N	UV-Vis(CHCl₃), λ_max/nm	IR(KBr), $ν ˙$ /cm^-1
PDI-ATPA	80.62(80.52)		5.41(5.27)		5.63(5.73)		304, 460, 491, 527	2958, 2925, 2856, 1700, 1660, 1591, 1497, 1340, 750
PDI-TATPA	78.12(78.38)		5.15(5.02)		5.64(5.74)		310, 464, 493, 530	2954, 2925, 2858, 1697, 1656, 1589, 1502, 1340, 744

Table 1 Elemental analysis, UV-Vis, and IR data of PDI-ATPA and PDI-TATPA

Compd.		Elemental analysis(%, calcd.)					UV-Vis(CHCl₃), λ_max/nm	IR(KBr), $ν ˙$ /cm^-1
Compd.		C		H		N	UV-Vis(CHCl₃), λ_max/nm	IR(KBr), $ν ˙$ /cm^-1
PDI-ATPA	80.62(80.52)		5.41(5.27)		5.63(5.73)		304, 460, 491, 527	2958, 2925, 2856, 1700, 1660, 1591, 1497, 1340, 750
PDI-TATPA	78.12(78.38)		5.15(5.02)		5.64(5.74)		310, 464, 493, 530	2954, 2925, 2858, 1697, 1656, 1589, 1502, 1340, 744

Table 2 1H NMR data of PDI-ATPA and PDI-TATPA

Compd.	¹H NMR(400 MHz, CDCl₃), δ
PDI-ATPA	8.71—8.59(m, 8H, PhH), 7.30(t, 4H, J=7.8 Hz, PhH), 7.21(d, 8H, J=7.4 Hz, PhH), 7.07(t, 2H, J=7.2 Hz, PhH), 4.16(t, 2H, J=8.0 Hz, CH₂), 1.97(s, 1H, CH), 1.42—1.32(m, 8H, CH₂), 0.89(t, 6H, J=7.4 Hz, CH₃)
PDI-TATPA	8.41—8.13(m, 24H, PhH), 7.41—7.34(m, 12H, PhH), 4.15(t, 6H,J=8.6 Hz, CH₂), 1.92(s, 3H, CH), 1.42—1.33(m, 24H, CH₂), 0.91(t, 18H, J=7.2 Hz, CH₃)

Scheme 1 Synthetic routes of PDI-ATPA and PDI-TATPA

Fig.1 Normalized UV-Vis absorption spectra of AsPDA-Ⅰ(a), PDI-ATPA(b) and PDI-TATPA(c) in CHCl3 c(CHCl3)=1×10-5 mol/L.

Table 3 Optical data of AsPDA-Ⅰ, PDI-ATPA and PDI-TATPA

Compd.	λ_{abs. max}/nm	λ_{em. max}/nm	ε_max/(cm^-1·L·mol^-1)	λ_edge/nm	$E g a$ /eV	△λ/nm	φ^b
AsPDA-Ⅰ	522	535	164200	555	2.23	13	0.99
PDI-ATPA	527	537	109000	587	2.11	10	0.02
PDI-TATPA	530	539	122000	612	2.03	9	0.01

Table 3 Optical data of AsPDA-Ⅰ, PDI-ATPA and PDI-TATPA

Compd.	λ_{abs. max}/nm	λ_{em. max}/nm	ε_max/(cm^-1·L·mol^-1)	λ_edge/nm	$E g a$ /eV	△λ/nm	φ^b
AsPDA-Ⅰ	522	535	164200	555	2.23	13	0.99
PDI-ATPA	527	537	109000	587	2.11	10	0.02
PDI-TATPA	530	539	122000	612	2.03	9	0.01

Fig.2 Normalized UV-Vis absorption(a) and flourescence emission spectra(b) of AsPDA-Ⅰ(A), PDI-ATPA(B) and PDI-TATPA(C) in CHCl3 c(CHCl3)=1×10-5 mol/L, λexcit.=485 nm.

Fig.3 UV-Vis absorption spectra of PDI-ATPA(A) and PDI-TATPA(B) in CHCl3 with different concentrations c/(mol·L-1): a. 1×10-6; b. 5×10-6; c. 1×10-5; d. 2×10-5.

Table 4 Molecular simulation results of AsPDA- I, PDI-ATPA and PDI-TATPA

Compd.	Energy gap/eV	Diploe moment
AsPDA-Ⅰ	2.79	4.1594
PDI-ATPA	1.92	0.7271
PDI-TATPA	2.06	0.4360

参考文献 23

[1]	Huang C., Barlow S., Marder S. R., J. Org. Chem., 2011, 76(8), 2386—2407
[2]	Doossel L. F., Kamm V., Howard I. A., Laquai F., Pisula W., Feng X., Muullen K., J. Am. Chem. Soc., 2012, 134(13), 5876—5886
[3]	Wurthner F., Chem. Commun., 2004, 5(14), 1564—1579
[4]	Ramanan C., Smeigh A. L., Anthony J. E., Marks T. J., Wasielewski M. R., J. Am. Chem. Soc., 2011, 134(1), 386—397
[5]	Huang J. C., Li H. Y., Mo X., Shi M. M., Wang M., Chen H. Z., Chem. Res. Chinese Universities,2014, 30(1), 63—67
[6]	Kozma E., Catellani M., Dyes Pigments,2013, 98(1), 160—179
[7]	Wang C. L., Dong H. L., Hu W. P., Liu Y. Q., Zhu D. B., Chem. Rev., 2012, 112(4), 2208—2267
[8]	Belfield K. D., Bondar M. V., Hernandez F. E., Przhonska O. V., J. Phys. Chem. C,2008, 112(14), 5618—5622
[9]	Wang T. Y., Hu X. X., Sun H. Y., Guo J. F., Liu D. Z., Li W., Wang L. C., Zhou X. Q., Chem. J. Chinese Universities,2014, 35(8), 1753—1760
	(汪天洋, 胡晓霞, 孙海亚, 郭建峰, 刘东志, 李巍, 王丽昌, 周雪琴. 高等学校化学学报,2014, 35(8), 1753—1760)
[10]	Ding L. W., Yang X. G., Zhong W. B., Liu C., Liu Z. H., Zhang F. J., Chem. J. Chinese Universities,2013, 34(5), 1277—1283
	(丁立伟, 杨新国, 钟文斌, 刘存, 刘振辉, 张凤菊. 高等学校化学学报,2013, 34(5), 1277—1283)
[11]	Pasaogullari N., Icil H., Demuth M., Dyes Pigments,2006, 69(3), 118—127
[12]	Nagao Y., Naito T., Abe Y., Misono T., Dyes Pigments,1996, 32(2), 71—83
[13]	Asir S., Demir A. S., Icil H., Dyes Pigments,2010, 84(1), 1—13
[14]	Zhang K., Niu H. J., Wang C., Bai X. D., Lian Y. F., Wang W., J. Electroanal. Chem., 2012, 682(6), 101—109
[15]	Li G. Y., Zhang B., Yan J., Wang Z. G., J. Mater. Chem. A,2014, 2(44), 18881—18888
[16]	Iverson I. K., Tam-Chang S. W., J. Am. Chem. Soc., 1999, 121(24), 5801—5802
[17]	Wang W., Li L. S., Helms G., Zhou H. H., Li A. D., J. Am. Chem. Soc., 2003, 125(5), 1120—1121
[18]	Liu Y., Wang K. R., Guo D. S., Jiang B. P., Adv. Funct. Mater., 2009, 19(14), 2230—2235
[19]	Wang W., Han J. J., Wang L. Q., Li L. S., Shaw W. J., Li A. D., Nano Lett., 2003, 3(4), 455—458
[20]	Rybtchinski B., Sinks L. E., Wasielewski M. R., J. Phys. Chem. A,2004, 108(37), 7497—7505
[21]	Adachi M., Murata Y., Nakamura S., J. Phys. Chem., 1995, 99(39), 14240—14246
[22]	Iverson I. K., Casey S. M., Seo W., Tam-Chang S. W., Pindzola B. A., Langmuir, 2002, 18(9), 3510—3516
[23]	Li X., Sinks L. E., Rybtchinski B., Wasielewski M. R., J. Am. Chem. Soc., 2004, 126(35), 10810—10811

含三苯胺结构的非对称型苝酰亚胺的合成及性能

Synthesis and Properties of Triphenylamine-containing Asymmetrical Perylene Diimides^†

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含三苯胺结构的非对称型苝酰亚胺的合成及性能

Synthesis and Properties of Triphenylamine-containing Asymmetrical Perylene Diimides†

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Synthesis and Properties of Triphenylamine-containing Asymmetrical Perylene Diimides^†