Bay区取代苝二酰亚胺分子构型及聚集调控:邻位甲基位阻效应

doi:10.7503/cjcu20170387

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (10): 1757.doi: 10.7503/cjcu20170387

Bay区取代苝二酰亚胺分子构型及聚集调控:邻位甲基位阻效应

张文强^1,², 周家东², 马炜涛², 朱娜², 解增旗²(), 刘琳琳², 马於光²()

1. 吉林大学超分子结构与材料国家重点实验室, 长春 130012
2. 华南理工大学发光材料与器件国家重点实验室, 广州 510640

收稿日期:2017-06-19 出版日期:2017-10-10 发布日期:2017-09-20
作者简介:联系人简介: 解增旗, 男, 博士, 教授, 博士生导师, 主要从事光电功能材料研究. E-mail:msxiez@scut.edu.cn;马於光, 男, 博士, 教授, 博士生导师, 主要从事光电功能材料研究. E-mail:ygma@scut.edu.cn
基金资助:
国家自然科学基金(批准号: 51373054, 51573055)、国家重点基础研究发展计划(批准号: 2014CB643504)和广州市科技计划项目(批准号: 201707020024)资助

Molecular Conformation and Aggregation Regulation of Bay-substituted Perylene Bismides: ortho-Methyl Steric Hindrance^†

ZHANG Wenqiang^1,², ZHOU Jiadong², MA Weitao², ZHU Na², XIE Zengqi^2,^*(), LIU Linlin², MA Yuguang^2,^*()

1. State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, China
2. State Key Laboratory of Luminescent Materials and Devices,South China University of Technology, Guangzhou 510640, China

Received:2017-06-19 Online:2017-10-10 Published:2017-09-20
Contact: XIE Zengqi,MA Yuguang E-mail:msxiez@scut.edu.cn;ygma@scut.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51373054, 51573055), the National Basic Research Program of China(No.2014CB643504) and the Science and Technology Program of Guangzhou, China (No.201707020024)

摘要/Abstract

摘要：

设计并合成了2种苝二酰亚胺分子PBI1和PBI2, 研究了bay区的苯氧基团邻位甲基取代对分子构型及分子聚集的影响. 通过对单晶结构的分析, 发现邻位甲基的引入明显影响苝二酰亚胺分子构型, 使得4个苯氧基呈中心对称分布. 由于甲基的空间位阻效应, 有效地减弱了分子间π-π相互作用, 从而提高了分子的溶解性与溶液加工成膜性. 研究结果表明, 在π共轭分子结构中的关键位置引入小的甲基取代基能够显著调控分子的聚集行为, 有效减少光电材料分子中非光电活性(增溶性基团)的含量, 对光电材料分子的设计合成具有重要的指导意义.

关键词: 苝二酰亚胺, 空间位阻, 聚集, 分子构型, 邻位甲基取代

Abstract:

The introduction of optoelectronically inactive long chain alkyl substituents commonly used to improve the solubility and film processing can inhibit intermolecular charge transfer in organic semiconductors. Therefore, to decrease the inactive alkyl substituents is important for next generation semiconductors. Herein, we designed and synthesized two perylene bisimide derivatives (PBI1 and PBI2) and investigated the effect of ortho-methylphenyoxyl substituent in bay area on molecular conformation and packing modes in the solid-state. The single crystal analysis confirmed that introduction of CH₃ could significantly affect the molecular conformation of PBI, leading to cross-style four phenoxyl groups. The steric hindrance of CH₃ inhibited the intermolecular π-π stacking, increased the solubility and enhanced the film-forming characters. The results show that CH₃ at the key positions of π-conjugated skeleton could effectively regulate the molecular aggregation. The strategy provides an excellent method to enhance the film processing and decrease the optoelectronic inactive alkyl substituents, therefore an important step forward for the design of new optoelectronic materials.

Key words: Perylene bisimide, Steric hindrance, Aggregation, Molecular conformation, ortho-Methyl substituent

中图分类号:

O621
O649.5

TrendMD:

张文强, 周家东, 马炜涛, 朱娜, 解增旗, 刘琳琳, 马於光. Bay区取代苝二酰亚胺分子构型及聚集调控:邻位甲基位阻效应. 高等学校化学学报, 2017, 38(10): 1757.

ZHANG Wenqiang, ZHOU Jiadong, MA Weitao, ZHU Na, XIE Zengqi, LIU Linlin, MA Yuguang. Molecular Conformation and Aggregation Regulation of Bay-substituted Perylene Bismides: ortho-Methyl Steric Hindrance^†. Chem. J. Chinese Universities, 2017, 38(10): 1757.

图/表 9

Fig.1 Molecular structures of PBI1(A) and PBI2(B)

Fig.2 Crystal structure of PBI1 from front view(A) and side view(B), side view along N—N direction(C), packing styles between two adjacent PBI molecules from side view(D) and top view(E) Hydrogen atom omitted in (A, B); butyl-substituents omitted for simplicity in (C); phenoxyl substituents omitted here for simplicity(E).

Scheme 1 Packing styles of PBI1 and PBI2 with different molecular conformations

Fig.3 TGA thermograms of PBI1 and PBI2 measured under nitrogen flow (20 mL/min) at a heating rate of 10 ℃/min(A) and DSC curves of PBI1(B) and PBI2(C), respectively measured under nitrogen flow at a heating rate of 10 ℃/min and a cooling rate of 5 ℃/min

Fig.4 UV-Vis absorption(A) and PL spectra(B) of PBI1 and PBI2 in solution and film state, in 1.5×10-5 mol/L chloroform and temperature-dependent UV-Vis absorption spectra of PBI1(C) and PBI2(D) in 10-4 mol/L methylcyclohexane

Fig.5 Cyclic voltammogram (CV) curves of PBI1 and PBI2 in dichloromethane, 0.1 mol/L n-Bu4NPF6 as electrolyteInset: CV curves of Fc/Fc+, 298 K, scan rate: 50 mV/s.

Table 1 Summary of optical properties and energy levels of PBI1 and PBI2

Sample	λ_abs /nm		λ_em/nm		E_HOMO/eV		E_LUMO/eV
Sample	Solution	Film	Solution	Film	Cyclic voltammetry method	B3LYP/ 6-31G(d,p)	Cyclic voltammetry method	B3LYP/ 6-31G(d,p)
PBI1	572	601	608	666	-5.57	-5.27	-3.78	-2.96
PBI2	572	446	603	622	-5.62	-5.29	-3.81	-2.97

Fig.6 AFM images of PBI1(A) and PBI2(B) films and SEM images of PBI1(C) and PBI2(D) films

Fig.7 XRD patterns of PBI1(a) and PBI2(b) films on quartz plate spin-coated from 5 mg/mL chloroform at rotating speed of 1500 r/min

参考文献 20

[1]	Burroughes J. H., Bradley D. D. C., Brown A. R., Marks R. N., Mackay K., Friend R. H., Burns P. L., Holmes A. B., Nature,1990, 347, 539—541
[2]	Zhan C. L., Yao J. N., Chem. Mater., 2016, 28, 1948—1964
[3]	Neill. M. O., Kelly. S. M., Adv. Mater., 2011, 23, 566—584
[4]	Rodriguez D. G., Schenning A. P. H. J., Chem. Mater., 2011, 23, 310—325
[5]	Würthner F. Kaiser T. E., Saha-Möller C. R., Angew. Chem. Int. Ed., 2011, 50, 3376—3410
[6]	Würthner F.,Chem. Commun., 2004, 1564—1579
[7]	Würthner F., Saha-Möller C. R., Fimmel B., Ogi S., Leowanawat P., Schmidt D., Chem. Rev., 2016, 116, 962—1052
[8]	Meng D., Sun D., Zhong C. M., Liu T., Fan B. B., Huo L. J., Li Y., Jiang W., Choi H. S., Kim T., Kim J. Y., Sun Y. M., Wang Z. H., Heeger A. J., J. Am. Chem. Soc., 2016, 138, 375—380
[9]	Jiang W., Ye L., Li X. G., Xiao C. Y., Tan F., Zhao W. C., Hou J. H., Wang Z. H., Chem. Commun., 2014, 1024—1026
[10]	Zhang X., Lu Z. H., Ye L., Zhan C. L., Hou J. H., Zhao S. Q., Jiang B., Zhao Y., Huang J. H., Zhang S. L., Liu Y., Shi Q., Liu Y. Q., Yao J. N., Adv. Mater., 2013, 25, 5791—5797
[11]	Schlosser F., Stepanenko V., Würthner F.,Chem. Commun., 2010, 8350—8352
[12]	Gao J., Xiao C. Y., Jiang W., Wang Z. H., Org. Lett., 2014, 16, 394—397
[13]	Kasha M., Rawls H. R., Ashraf El-Bayoumi M., Pure Appl. Chem., 1965, 11, 371—392
[14]	Wu H. X., Xue L., Shi Y., Chen Y. L., Li X. Y., Langmuir,2011, 27, 3074—3082
[15]	Xie Z. Q., Würthner F., Org. Lett., 2010, 12, 3204—3207
[16]	Toda A., Taguchi K., Nozaki K., Konishi M., Polymer,2014, 55, 3186—3194
[17]	Kaiser T. E., Stepanenko V., Würthner F., J. Am. Chem. Soc., 2009, 131, 6719—6732
[18]	Wang H., Kaiser T. E., Uemura S., Würthner F.,Chem. Commun., 2008, 1181—1183
[19]	Yagai S., Seki T., Karatsu T., Kitamura A., Würthner F., Angew. Chem. Int. Ed., 2008, 47, 3367—3371
[20]	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)

Bay区取代苝二酰亚胺分子构型及聚集调控:邻位甲基位阻效应

Molecular Conformation and Aggregation Regulation of Bay-substituted Perylene Bismides: ortho-Methyl Steric Hindrance^†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 20

相关文章 15

编辑推荐

Metrics

本文评价

[1]	赵永梅, 穆叶舒, 洪琛, 罗稳, 田智勇. 双萘酰亚胺衍生物用于检测水溶液中的苦味酸[J]. 高等学校化学学报, 2022, 43(3): 20210765.
[2]	伍泽鑫, 朱渊杰, 王泓中, 王均安, 贺英. 甲基修饰的咔唑/二苯砜基AIE-TADF蓝光材料及其OLED器件[J]. 高等学校化学学报, 2022, 43(11): 20220371.
[3]	刘威, 姚伟, 周明明, 游淇, 聂永, 蒋绪川. 9,10⁃二(N⁃苯基吲哚⁃3⁃乙烯基)蒽的合成及聚集诱导荧光和压致荧光变色性质[J]. 高等学校化学学报, 2021, 42(8): 2668.
[4]	李根, 王克亮, 逯春晶. 颗粒聚集体对两性SiO₂颗粒无水泡沫表面性质的影响[J]. 高等学校化学学报, 2020, 41(9): 2038.
[5]	李红红,耿科颖,田芙月,顾芳,王海军. 偶极Janus粒子的相态结构调控及应用[J]. 高等学校化学学报, 2020, 41(5): 1042.
[6]	李婧影, 陈琛, 李娟, 杨黄浩. 人工调控细胞表面受体聚集状态及功能[J]. 高等学校化学学报, 2020, 41(5): 892.
[7]	白兰, 翟磊, 王畅鸥, 何民辉, 莫松, 范琳. 含酰胺结构超低膨胀聚酰亚胺薄膜的热膨胀行为[J]. 高等学校化学学报, 2020, 41(4): 795.
[8]	杜宪超, 郝红霞, 秦安军, 唐本忠. 聚集诱导发光分子/适配体/外切酶Ⅰ体系对可卡因的检测[J]. 高等学校化学学报, 2020, 41(3): 411.
[9]	武文博,刘斌. 可双光子激发的聚集诱导发光光敏剂及其生物医学应用[J]. 高等学校化学学报, 2020, 41(2): 191.
[10]	姜童, 任佳骏, 帅志刚. 频域空间密度矩阵重正化群的研究进展[J]. 高等学校化学学报, 2020, 41(12): 2610.
[11]	刘秋娜, 许文文, 刘茂祝, 王惠钢, 郑旭明. 高分辨偏正拉曼光谱对丙酸酐C=O振动模的拉曼光谱非一致效应研究[J]. 高等学校化学学报, 2019, 40(5): 932.
[12]	张雨, 荆江博, 邵玥明, 殷鑫, 徐斌, 温晓玉. 基于聚集诱导发光的纳米粒子用于肝癌细胞靶向成像[J]. 高等学校化学学报, 2019, 40(11): 2382.
[13]	魏良晨, 胡伟康, 周世雄, 束俊, 周会东, 胡旭成, 姜毅, 童碧海, 张千峰. 含亚磷酸酯和联吡啶羧酸酯配体的铱配合物及其聚集诱导发光增强和电致发光性能[J]. 高等学校化学学报, 2018, 39(7): 1371.
[14]	凌瑶, 刘雪静, 郝海景, 郝晓辉, 白利斌, 武永刚. 具有聚集诱导发光效应的水溶性糖基荧光聚合物的制备及性能[J]. 高等学校化学学报, 2018, 39(6): 1319.
[15]	张焕, 董晓燕. EGCG对β-淀粉样蛋白聚集的抑制作用: pH的影响[J]. 高等学校化学学报, 2018, 39(11): 2534.

Bay区取代苝二酰亚胺分子构型及聚集调控:邻位甲基位阻效应

Molecular Conformation and Aggregation Regulation of Bay-substituted Perylene Bismides: ortho-Methyl Steric Hindrance†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 20

相关文章 15

编辑推荐

Metrics

本文评价

Molecular Conformation and Aggregation Regulation of Bay-substituted Perylene Bismides: ortho-Methyl Steric Hindrance^†