Regulating Optical Properties of Water-Soluble Conjugated Polythiophene with Polyvinyl Alcohol

doi:10.6023/A22010013

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (7): 921-928.DOI: 10.6023/A22010013 Previous Articles Next Articles

Article

聚乙烯醇调控水溶性共轭聚噻吩的光学性质

齐子朋^a, 高冬^b, 朱志成^d, 贺志远^c^,^*(), 白国英^a^,^*()

a 河北工业大学材料科学与工程学院天津 300401
b 河北工业大学生物物理研究所天津 300401
c 北京理工大学材料学院北京 100081
d 中能电力科技开发有限公司北京 100034

投稿日期:2022-01-08 发布日期:2022-04-05
通讯作者: 贺志远, 白国英
基金资助:
国家重点研发计划国际合作项目(2020YFE0100300); 国家自然科学基金(22072036); 国家自然科学基金(21905072); 国家自然科学基金(22122206); 天津市自然科学基金(20JCQNJC00890); 河北省自然科学基金(B2020202034); 河北省自然科学基金(B2020202086); 河北省高等学校科学技术研究(BJ2020039)

Regulating Optical Properties of Water-Soluble Conjugated Polythiophene with Polyvinyl Alcohol

Zipeng Qi^a, Dong Gao^b, Zhicheng Zhu^d, Zhiyuan He^c(), Guoying Bai^a()

a School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300401
b Institute of Biophysics, Hebei University of Technology, Tianjin 300401
c School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081
d Zhongneng Power-Tech Development Co., Ltd., Beijing 100034

Received:2022-01-08 Published:2022-04-05
Contact: Zhiyuan He, Guoying Bai
Supported by:
National Key Research and Development Program of China(2020YFE0100300); National Natural Science Foundation of China(22072036); National Natural Science Foundation of China(21905072); National Natural Science Foundation of China(22122206); Natural Science Foundation of Tianjin(20JCQNJC00890); Natural Science Foundation of Hebei Province(B2020202034); Natural Science Foundation of Hebei Province(B2020202086); Science and Technology Research Project of Higher Education in Hebei Province(BJ2020039)

1. .pdf(1277KB)

Abstract

Water-soluble conjugated polymers have attracted enormous attention because of their water solubility and attractive optical properties. However, they often suffer from low emission quantum yield due to their strong inter-chain interaction and concomitant exciton quenching, especially in the solid state. To enhance the emission of the water-soluble conjugated polymers, strategies of decreasing the aggregation tendency of the polymers and controlling the backbone conformations are often adopted. In this work, to solve the problem of aggregation-caused quenching of luminescent conjugated polymer dilute solution during drying, we regulate the aggregation behavior and backbone conformation of a water-soluble conjugated polythiophene (PMNT) with polyvinyl alcohol (PVA) by intermolecular interactions, e.g. hydrogen bonding, and obtained tunable emissive PMNT thin films. Specifically, when PMNT in solution state is blended with PVA, obvious red shift of absorption and emission maxima and higher fluorescence intensity are observed, indicating that PVA molecules isolate the PMNT chains, reduce the degree of chain flexibility and increase backbone rigidity. Furthermore, by varying dry methods, we obtained PMNT solid films of tunable light absorption/emission properties: the solid films fabricated through splat cooling and in-situ lyophilization preserve the optical properties of the mixed solution of PVA and PMNT; the films fabricated through heat drying exhibit the similar optical properties with those of PMNT solution without adding PVA. Moreover, the emission quantum yield of the solid film prepared by the lyophilization method was enhanced compared with that of the solid film prepared by heat drying. These results suggest that the aggregation/conformation regulations of PMNT solution by PVA are retained in different degrees dependent on the drying methods: heat drying only maintains the isolation effect of PVA on PMNT; lyophilization readily preserve the interactions between PVA and PMNT, locking their disperse states and conformations. This study provides a strategy for regulating the aggregation behaviors and optical properties of solid conjugated polymers from the perspective of drying method.

Key words: water-soluble conjugated polymer, optical property, aggregation behavior, freeze drying

Cite this article

Zipeng Qi, Dong Gao, Zhicheng Zhu, Zhiyuan He, Guoying Bai. Regulating Optical Properties of Water-Soluble Conjugated Polythiophene with Polyvinyl Alcohol[J]. Acta Chimica Sinica, 2022, 80(7): 921-928.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

Figure 1. Optical property characterizations of PMNT solution or film: (a) UV-Vis absorption spectra, (b) fluorescence emission spectra and absolute quantum yield, (c) bright field/fluorescence images; Optical property characterizations of PMNT+PVA solution/film (obtained by freeze drying (FD)/heat drying (HD)): (d) UV-Vis absorption, (e) fluorescence emission spectrum and absolute quantum yield, (f) bright field/fluorescence images (cPMNT=0.05 g/L, cPVA∶cPMNT=200)

Figure 2. Optical properties of PMNT and PVA mixed solutions at various concentration ratios: (a) UV-Vis absorption spectra (the inset shows color change of PMNT+PVA solution under different mixing ratios, the ratio of PVA increases from left to right); (b, c) fluorescence emission spectra and (d) fluorescence intensity of PMNT+PVA solution

Figure 3. Optical properties of PMNT+PVA (HD): (a) UV-vis spectra; (b) fluorescence emission spectra; (c) bright field (B)/fluorescence (F) image

Figure 4. Optical properties of PMNT+PVA solution at different temperatures: (a) UV-Vis absorption spectra, the inset is the photos of PMNT+PVA solutions; (b) fluorescence emission spectra, the inset is the images of fluorescence microscope

Figure 5. Optical properties of PMNT+PVA (FD): (a) UV-Vis spectra; (b) fluorescence emission spectra; (c) bright field/fluorescence images

Figure 6. Mechanism of the PMNT luminescence property regulation by PVA under solution or solid state conditions

References 37

[1]	Feng, X. L.; Liu, L. B.; Wang, S.; Zhu, D. B. Chem. Soc. Rev. 2010, 39, 2411. doi: 10.1039/b909065g
[2]	Pankow, R. M.; Thompson, B. C. Polymer 2020, 207, 23.
[3]	Zhu, C. L.; Liu, L. B.; Yang, Q.; Lv, F. T.; Wang, S. Chem. Rev. 2012, 112, 4687. doi: 10.1021/cr200263w
[4]	Xu, W. D.; Lai, W. Y.; Fan, Q. L.; Huang, W. Sci. Sin. Chim. 2011, 41, 409. (in Chinese) doi: 10.1360/032010-716
	(徐巍栋, 赖文勇, 范曲立, 黄维, 中国科学:化学, 2011, 41, 409.)
[5]	Zhang, E. D.; Liu, L. B.; Lv, F. T.; Wang, S. Acta Polym. Sin. 2018, (2), 186. (in Chinese)
	(张恩东, 刘礼兵, 吕凤婷, 王树, 高分子学报, 2018, (2), 186.)
[6]	Du, J. P.; Qin, P. J.; Xu, L. C.; Feng, S. S.; Xu, Y. X.; Huang, J. Chin. J. Org. Chem. 2020, 40, 194. (in Chinese) doi: 10.6023/cjoc201907001
	(杜俊平, 秦鹏举, 绪连彩, 封珊珊, 徐云祥, 黄江, 有机化学, 2020, 40, 194.) doi: 10.6023/cjoc201907001
[7]	Liu, X. F.; Wang, Y. T.; Huang, Y. Q.; Feng, X. M.; Fan, Q. L.; Huang, W. Acta Chim. Sinica 2016, 74, 664. (in Chinese) doi: 10.6023/A16040205
	(刘兴奋, 王亚腾, 黄艳琴, 冯晓苗, 范曲立, 黄维, 化学学报, 2016, 74, 664.) doi: 10.6023/A16040205
[8]	Zhou, X. Y.; Zhao, J. W.; Ma, G. M.; Jia, H. X. Chin. J. Chem. 2019, 47, 1006.
[9]	Al-Attar, H. A.; Monkman, A. P. Adv. Funct. Mater. 2012, 22, 3824. doi: 10.1002/adfm.201200814
[10]	Li, Z. L.; Acharya, R.; Wang, S. S.; Schanze, K. S. J. Mater. Chem. C 2018, 6, 3722. doi: 10.1039/C7TC05081J
[11]	Jagadesan, P.; Yu, Z. Q.; Barboza-Ramos, I.; Lara, H. H.; Vazquez-Munoz, R.; Lopez-Ribot, J. L.; Schanze, K. S. Chem. Mater. 2020, 32, 6186. doi: 10.1021/acs.chemmater.0c02076
[12]	Liu, X. F.; Cai, X. H.; Huang, Y. Q.; Shi, L.; Fan, Q. L.; Huang, W. Acta Chim. Sinica 2014, 72, 440. (in Chinese) doi: 10.6023/A13121247
	(刘兴奋, 蔡小慧, 黄艳琴, 石琳, 范曲立, 黄维, 化学学报, 2014, 72, 440.) doi: 10.6023/A13121247
[13]	Alizadeh, N.; Akbarinejad, A.; Hosseinkhani, S.; Rabbani, F. Anal. Chim. Acta 2019, 1084, 99. doi: S0003-2670(19)30921-3 pmid: 31519240
[14]	Lv, S. Y.; Li, L.; Mu, Y. B.; Wan, X. B. Polym. Rev 2021, 61, 520. doi: 10.1080/15583724.2020.1855195
[15]	Hu, Z. C.; Wang, Z. F.; Zhang, X.; Tang, H. R.; Liu, X. C.; Huang, F.; Cao, Y. iScience 2019, 13, 33. doi: 10.1016/j.isci.2019.02.007
[16]	Yin, C.; Tai, X. Y.; Li, X. Z.; Tan, J. H.; Lee, C. S.; Sun, P. F.; Fan, Q. L.; Huang, W. Chem. Eng. J. 2022, 428, 9.
[17]	Pei, T.; Peng, K.; Cai, X. Y.; Yuan, L. J.; Xia, J. B. Acta Phys.-Chim. Sin. 2017, 33, 2550 (In Chinese).
	(裴童, 彭凯, 蔡心怡, 袁良杰, 夏江滨, 物理化学学报, 2017, 33, 2550.)
[18]	Cui, Q. L.; Xu, J. S.; Shen, G. Z.; Zhang, C.; Li, L. D.; Antonietti, M. ACS Appl. Mater. Inter. 2017, 9, 43966. doi: 10.1021/acsami.7b13212
[19]	Pal, S.; Roy, D.; Mondal, M. K.; Chowdhury, P. J. Polym. Res. 2019, 26, 9. doi: 10.1007/s10965-018-1622-3
[20]	Long, S.; Wan, Y.; Xia, A. D. Acta Chim. Sinica 2015, 73, 723. (in Chinese) doi: 10.6023/A15030197
	(龙飒然, 宛岩, 夏安东, 化学学报, 2015, 73, 723.) doi: 10.6023/A15030197
[21]	Cui, Q. L.; He, F.; Wang, X. Y.; Xia, B. H.; Li, L. D. Abstracts of 2013 National Polymer Academic Paper Conference, Photoelectric Functional Polymer, Polymer Discipline Committee of Chinese Chemical Society, Chinese Chemical Society, 2013, p. 15. (in Chinese)
	(崔倩玲, 贺芳, 王晓瑜, 夏碧华, 李立东, 2013年全国高分子学术论文报告会论文摘要集, 中国化学会, 2013, p. 15.)
[22]	Zhu, S. X.; Wang, X. Y.; Yang, Y.; Bai, H. T.; Cui, Q. L.; Sun, H.; Li, L. D.; Wang, S. Chem. Mater. 2018, 30, 3244. doi: 10.1021/acs.chemmater.8b00164
[23]	Donabedian, P. L.; Creyer, M. N.; Monge, F. A.; Schanze, K. S.; Chi, E. Y.; Whitten, D. G. Proc. Natl. Acad. Sci. U. S. A. 2017, 114, 7278. doi: 10.1073/pnas.1702513114 pmid: 28642346
[24]	Tang, Y. L.; Zhou, Z. J.; Ogawa, K.; Lopez, G. P.; Schanze, K. S.; Whitten, D. G. J. Photochem. Photobiol. A-Chem. 2009, 207, 4. doi: 10.1016/j.jphotochem.2009.03.006
[25]	Hill, E. H.; Sanchez, D.; Evans, D. G.; Whitten, D. G. Langmuir 2013, 29, 15732. doi: 10.1021/la4038827
[26]	Hill, E. H.; Zhang, Y.; Evans, D. G.; Whitten, D. G. ACS Appl. Mater. Inter. 2015, 7, 5550. doi: 10.1021/acsami.5b00185
[27]	Wurthner, F.; Kaiser, T. E.; Saha-Moller, C. R. Angew. Chem., Int. Ed. 2011, 50, 3376. doi: 10.1002/anie.201002307
[28]	Du, C. S.; Gao, D.; Gao, M. S.; Yuan, H. B.; Liu, X. N.; Wang, B.; Xing, C. F. ACS Appl. Mater. Inter. 2021, 13, 27955. doi: 10.1021/acsami.1c06659
[29]	Geoghegan, M.; Krausch, G. Prog. Polym. Sci. 2003, 28, 261. doi: 10.1016/S0079-6700(02)00080-1
[30]	Wei, H. T.; Jin, G.; Wang, L.; Hao, L.; Na, T. Y.; Wang, Y.; Tian, W. J.; Sun, H. Z.; Zhang, H. X.; Wang, H. Y.; Zhang, H.; Yang, B. Adv. Mater. 2014, 26, 3655. doi: 10.1002/adma.201305500
[31]	Gu, Z.; Shen, Q. D.; Zhang, J.; Yang, C. Z.; Bao, Y. J. J. Appl. Polym. Sci. 2006, 100, 2930. doi: 10.1002/app.22510
[32]	Knaapila, M.; Stewart, B.; Costa, T.; Rogers, S. E.; Pragana, J.; Fonseca, S. M.; Valente, A. J. M.; Ramos, M. L.; Murtinho, D.; Pereira, J. C.; Mallavia, R.; Burrows, H. D. Macromolecules 2016, 49, 9119. doi: 10.1021/acs.macromol.6b01895
[33]	Al-Attar, H. A.; Monkman, A. P. Phys. Rev. B 2012, 86, 235420. doi: 10.1103/PhysRevB.86.235420
[34]	Brustolin, F.; Goldoni, F.; Meijer, E. W.; Sommerdijk, N. A. J. M. Macromolecules 2002, 35, 1054. doi: 10.1021/ma011334r
[35]	Yuan, H. B.; Zang, Y.; Rowan, A. E.; Kouwer, P. H. J.; Xing, C. F. Angew. Chem., Int. Ed. 2020, 59, 2720. doi: 10.1002/anie.201910979
[36]	Ho, H. A.; Boissinot, M.; Bergeron, M. G.; Corbeil, G.; Dore, K.; Boudreau, D.; Leclerc, M. Angew. Chem., Int. Ed. 2002, 41, 1548. doi: 10.1002/1521-3773(20020503)41:9【-逻辑与-】#x00026;lt;1548::AID-ANIE1548【-逻辑与-】#x00026;gt;3.0.CO;2-I
[37]	Park, S. Y.; Baik, H. J.; Oh, Y. T.; Oh, K. T.; Youn, Y. S.; Lee, E. S. Angew. Chem., Int. Ed. 2011, 50, 1644. doi: 10.1002/anie.201006038

聚乙烯醇调控水溶性共轭聚噻吩的光学性质

Regulating Optical Properties of Water-Soluble Conjugated Polythiophene with Polyvinyl Alcohol

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 37

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Xue Gong, Xinguo Ma, Fengda Wan, Wangyang Duan, Xiaoling Yang, Jinrong Zhu. Study on the Electronic Structure and Optical Properties of Two-dimensional Monolayer MoSi₂X₄ (X=N, P, As) [J]. Acta Chimica Sinica, 2022, 80(4): 510-516.
[2]	Gao Simeng, Xia Kun, Kang Zhihong, Nai Yongning, Yuan Ruixia, Niu Ruixia. Molecular Dynamics Simulation of “Quasi-Gemini” Anionic Surfactant at the Decane/Water Interface [J]. Acta Chimica Sinica, 2020, 78(2): 155-160.
[3]	Liu Yanhong, Zhang Dongxu, Mao Baodong, Huang Hui, Liu Yang, Tan Huaqiao, Kang Zhenhui. Progress in Carbon Dots from the Perspective of Quantum Dots [J]. Acta Chimica Sinica, 2020, 78(12): 1349-1365.
[4]	Gao Zhen, Huang Kun, Du Lin, Liu Huizhou. Interfacial Behavior of Acidic Organophosphorus Extractant Monolayer at Air-Water Interface: Subphase pH and Spreading Solvent Effect [J]. Acta Chim. Sinica, 2019, 77(6): 506-514.
[5]	Huang Lu, Li Zhichun, Huang Shouqiang, Peter Reiss, Li Liang. Synthesis of InPZnS/ZnS Quantum Dots by Continuous Injection of Phosphorus Precursor [J]. Acta Chim. Sinica, 2017, 75(3): 300-306.
[6]	Liu Xingfen, Cai Xiaohui, Huang Yanqin, Shi Lin, Fan Quli, Huang Wei. Biotinylated Water-Soluble Conjugated Polymers：Synthesis and the Application in Biological Analysis [J]. Acta Chimica Sinica, 2014, 72(4): 440-446.
[7]	CHEN Zi-Ran, NIE Han, LI Quan, ZHAO Ke-Qing. Electronic spectrum and the secord-order nonlinear optical properties of pyrazoline- oxadiazole organic molecules [J]. Acta Chimica Sinica, 2011, 69(24): 2908-2914.
[8]	RONG Cheng, CAI Xiang-Yang, JIANG Jiang. Synthesis and First-Principle Calculation of Electronic Structure and Optical Properties of Low Temperature Phase GeO₂ Crystal [J]. Acta Chimica Sinica, 2011, 69(17): 1973-1979.
[9]	WEN Xin, WANG Su-Juan, GAO Bao-Xiang, BA Xin-Wu. Study of the Aggregation of Meso-tetrakis(4-hydroxyphenyl) porphyrin in the Hyperbranched Poly(amide-ester) Solution [J]. Acta Chimica Sinica, 2010, 68(18): 1876-1880.
[10]	CA Jing, CENG Wei, LI Quan, JIA Kai-Jun, DIAO Ge-Qing. DFT Studies on Electronic Spectrum and Second-order Nonlinear Optical Properties of 8-Quinolinolate Metal Complexes [J]. Acta Chimica Sinica, 2009, 67(20): 2301-2308.
[11]	Hu Jian-Hua. Mechanical and Optical Properties of PMMA Prepared by Modified Microemulsion Polymerization [J]. Acta Chimica Sinica, 2009, 67(12): 1370-1374.
[12]	LIU Zhong-Yi LI Yan-Jun HUANG Peng-Cheng*. Synthesis and Optical Properties of a Novel Low Band-Gap Conjugated Polymer [J]. Acta Chimica Sinica, 2008, 66(8): 999-1002.
[13]	. Quantum Chemistry Calculations of the Nonlinear Optical Properties of Gold Acetylide Complexes [J]. Acta Chimica Sinica, 2008, 66(17): 1935-1942.
[14]	CHEN, Jun-Rong XU, Bu-Yi CAI, Jing LI, Quan* LUO, Kai-Jun ZHAO, Ke-Qing . Theoretical Studies on Electronic Spectra and Second-order Nonlinear Optical Properties of Cyclometalated Platinum Complexes with Long Chain β-Diketonate Ancillary Ligands [J]. Acta Chimica Sinica, 2008, 66(13): 1513-1517.
[15]	LIU Bin; FENG Ji-Kang*^,1,2; REN Ai-Min; YANG Li; ZOU Lu-Yi. Theoretical Investigation on Electronic Structure and Optical Proper-ties of Polyfluorene by Copolymerization with Dibenzothiophene [J]. Acta Chimica Sinica, 2007, 65(8): 673-677.