供/吸电子基团共轭桥联的双BODIPY衍生物的合成及性能

doi:10.7503/cjcu20150034

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (6): 1094.doi: 10.7503/cjcu20150034

供/吸电子基团共轭桥联的双BODIPY衍生物的合成及性能

彭再喜^1,², 廖俊旭², 徐勇军², 赵鸿斌², 彭敏², 崔云增², 宁静恒¹

1. 长沙理工大学化学与生物工程学院, 长沙 410004
2. 东莞理工学院化学与环境工程学院, 东莞 523808

收稿日期:2015-01-12 出版日期:2015-06-10 发布日期:2015-05-15
作者简介:联系人简介: 宁静恒, 女, 博士, 副教授, 主要从事有机功能材料研究. E-mail:ningjingheng@126.com;廖俊旭, 男, 工程师, 主要从事有机功能材料研究. E-mail:liaojx83@126.com
基金资助:
国家自然科学基金(批准号: 21342003)、广东省自然科学基金(批准号: 2014A030313630)和广东省教育厅广东省高等学校高层次人才项目[批准号: 粤财教(2013) 246号]资助

Synthesis and Properties of Symmetrical Donor or Acceptor Unit Conjugate Linked BODIPY Derivatives^†

PENG Zaixi^1,², LIAO Junxu^2,^*, XU Yongjun², ZHAO Hongbin², PENG Min², CUI Yunzeng², NING Jingheng^1,^*

1. School of Chemical and Biological Engineering, Changsha University of Science and Technology, Changsha 410004, China
2. College of Chemistry and Environmental Engineering, Dongguan University of Technology, Dongguan 523808, China

Received:2015-01-12 Online:2015-06-10 Published:2015-05-15
Contact: LIAO Junxu,NING Jingheng
Supported by:
† Supported by the National Natural Science Foundation of China(No.21342003), the Natural Science Foundation of Guangdong Province, China(No.2014A030313630) and the Project for High-level Personnel of University in Guangdong Province, China(No.[2013]246)

摘要/Abstract

摘要：

设计合成了4种对称的以不同供/吸电子基团为共轭桥、两端连接meso位苯或噻吩取代的新型氟化硼二吡咯甲川(BODIPY)衍生物; 通过¹H NMR, ¹³C NMR和MS等手段对其进行了结构表征; 并采用紫外吸收光谱、荧光发射光谱及循环伏安(CV)等方法研究了其光电性能. 紫外光谱数据表明, BODIPY结构具有明显的特征吸收, 中间的桥联基团无论是强供电子的苯并二噻吩(BDT)还是强吸电子的苯并噻二唑(BT)均不能使整个分子产生明显的分子内电子迁移(ICT). 另一方面, meso位的取代基可与BODIPY核产生微弱的ICT, 且meso位噻吩取代的分子比meso位苯环取代的分子表现出更强的ICT. 紫外光谱数据和电化学测试结果表明, meso位噻吩取代的分子比meso位苯环取代的分子具有更低的氧化电位和更窄的能隙.

关键词: 氟化硼二吡咯甲川衍生物, 共轭桥, 供/吸电子基团, 光电性能

Abstract:

Four novel symmetrical 4,4'-difluoro-4-bora-3a,4a-diaza-sindacene(BODIPY) derivatives were synthesized. These BODIPY derivatives bear different donor or acceptor units as conjugate bridge, and the BODIPYs meso-position substituted by thiophene or benzene as the termini groups. The structures of all the compounds were identified by ¹H NMR, ¹³C NMR and MS techniques. The photophysical properties of these compounds were measured by the UV-Vis absorption and the fluorescence emission spectrophotometer. And the electrochemical properties were investigated by the cyclic voltammetry. The results of absorption spectra confirmed that these BODIPYs had a characteristic absorption peak, and the conjugate bridges had little influence on the intramolecular charge-transfer(ICT) interaction neither used as donor nor acceptor. On the other hand, meso-position substituentes have a weak influence on the ICT interaction in the BODIPYs, and meso-position thiophene substituted ones have raised more intensive ICT than the meso-position benzene substituted ones. Both the absorption spectra and cyclic voltammetry data indicate that BODIPYs with meso-thiophene substitutuents possess a lower oxidation potential and a narrower band gap than those meso-position benzene ones.

Key words: 4, 4'-Difluoro-4-bora-3a, 4a-diaza-sindacene(BODIPY) derivative, Conjugate bridge, Donor or acceptor unit, Photophysical property

中图分类号:

O621

TrendMD:

彭再喜, 廖俊旭, 徐勇军, 赵鸿斌, 彭敏, 崔云增, 宁静恒. 供/吸电子基团共轭桥联的双BODIPY衍生物的合成及性能. 高等学校化学学报, 2015, 36(6): 1094.

PENG Zaixi, LIAO Junxu, XU Yongjun, ZHAO Hongbin, PENG Min, CUI Yunzeng, NING Jingheng. Synthesis and Properties of Symmetrical Donor or Acceptor Unit Conjugate Linked BODIPY Derivatives^†. Chem. J. Chinese Universities, 2015, 36(6): 1094.

图/表 6

Scheme 1 Synthetic routes of compounds BDP1—BDP4

Table 1 Appearance, yields and melting points and MALDI-TOF-MS data for compounds BDP1—BDP4

Compd.	Appearance	Yield^*(%)	m. p./℃	MALDI-TOF-MS(calcd.), m/z
BDP1	Purple red solid	51.0	247—249	978.359(978.400)
BDP2	Blue solid	56.0	183—185	990.294(990.310)
BDP3	Orange red crystal	61.0	159—162	649.203(668.170)
BDP4	Blue purple solid	57.0	188—190	661.084(680.090)

Table 2 1H NMR and 13C NMR data for compounds BDP1—BDP4

Compd.	¹H NMR(600 MHz, CDCl₃), δ	¹³C NMR(151 MHz, CDCl₃), δ
BDP1	8.00(s, 4H), 7.94(d,J=8.2 Hz, 4H), 7.86(s, 2H), 7.71(d, J=8.2 Hz, 4H), 7.05(d, J=4.0 Hz, 4H), 6.61(d, J=4.0 Hz, 4H), 4.31(d, J= 5.5 Hz, 4H), 1.70(m, 2H), 1.27—1.22(m, 16H), 1.05—0.97(m, 12H)	146.48, 144.85, 144.27, 142.33, 136.87, 134.83, 133.74, 132.98, 131.32, 129.74, 126.36, 126.08, 118.63, 117.31, 40.73, 30.63, 29.68, 29.23, 24.03, 23.23, 14.07, 11.44
BDP2	7.98(s, 4H), 7.70(s, 2H), 7.60(d, J=3.9 Hz, 2H), 7.51(d, J=3.8 Hz, 2H), 7.40(d, J=4.1 Hz, 4H), 6.64(d, 4H), 4.27(d, J=5.4 Hz, 4H), 1.90(m, 2H), 1.41—1.20(m, 12H), 1.10—0.98(m, 12H)	144.67, 143.93 143.66 138.68, 125.50, 134.52, 134.24, 134.10, 132.76, 131.07, 129.61, 126.36, 118.58, 118.13, 40.74, 30.60, 29.66, 29.26, 23.83, 23.18, 14.28, 11.43
BDP3	8.24(d,J=8.1 Hz, 4H), 8.01(s, 4H), 8.00(s, 2H), 7.82(d, J=8.1 Hz, 4H), 7.11(d, J=4.0 Hz, 4H), 6.62(d, J=2.8 Hz, 4H)	153.93, 146.74, 144.32, 139.76, 134.95, 134.01, 132.76, 131.59, 130.92, 129.34, 128.56, 118.68
BDP4	8.28(d,J=4.0 Hz, 2H), 8.08(s, 2H), 7.97(s, 4H), 7.71(d, J=3.8 Hz, 2H), 7.42(d, J=3.5 Hz, 4H), 6.63(d, 4H)	151.42, 146.93, 143.35, 135.19, 132.27, 131.21, 130.53, 127.46, 125.35, 123.94, 122.10, 119.07

Table 3 Optical data of BDPs in dichloromethane solution and thin film on quartz surface

Compd.	$λ max a$ /nm	lgε_max	λ_max ^b/nm	λ_em/nm	Stokes-shift/cm^-1
BDP1	503	4.84	520	522	723.6
BDP2	516	4.33	536	556	1394.2
BDP3	503	4.98	530	533	1119.0
BDP4	517	5.91	571	614	3055.7

Table 3 Optical data of BDPs in dichloromethane solution and thin film on quartz surface

Compd.	$λ max a$ /nm	lgε_max	λ_max ^b/nm	λ_em/nm	Stokes-shift/cm^-1
BDP1	503	4.84	520	522	723.6
BDP2	516	4.33	536	556	1394.2
BDP3	503	4.98	530	533	1119.0
BDP4	517	5.91	571	614	3055.7

Fig.1 Optimized structures of compounds BDP1—BDP4

Table 4 Electrochemistry data of compounds BDPs*

Compd.	E_g/eV	$E onset red$ /V	$E p red$ /V	E_ox/V	E_HOMO/eV	E_LUMO/eV
BDP1	2.13	-0.78	-1.04	1.35	-5.62	-3.49
BDP2	1.85	-0.74	-1.01	1.11	-5.38	-3.53
BDP3	2.29	-0.66	-1.03	1.63	-5.95	-3.66
BDP4	1.97	-0.70	-1.04	1.27	-5.54	-3.57

Table 4 Electrochemistry data of compounds BDPs*

Compd.	E_g/eV	$E onset red$ /V	$E p red$ /V	E_ox/V	E_HOMO/eV	E_LUMO/eV
BDP1	2.13	-0.78	-1.04	1.35	-5.62	-3.49
BDP2	1.85	-0.74	-1.01	1.11	-5.38	-3.53
BDP3	2.29	-0.66	-1.03	1.63	-5.95	-3.66
BDP4	1.97	-0.70	-1.04	1.27	-5.54	-3.57

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供/吸电子基团共轭桥联的双BODIPY衍生物的合成及性能

Synthesis and Properties of Symmetrical Donor or Acceptor Unit Conjugate Linked BODIPY Derivatives^†

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供/吸电子基团共轭桥联的双BODIPY衍生物的合成及性能

Synthesis and Properties of Symmetrical Donor or Acceptor Unit Conjugate Linked BODIPY Derivatives†

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Synthesis and Properties of Symmetrical Donor or Acceptor Unit Conjugate Linked BODIPY Derivatives^†