The importance of sulfonate to the self-doping mechanism of the water-soluble conjugated polyelectrolyte PCPDTBT-SO3K,Materials Chemistry Frontiers

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The importance of sulfonate to the self-doping mechanism of the water-soluble conjugated polyelectrolyte PCPDTBT-SO3K
Materials Chemistry Frontiers ( IF 6.0 ) Pub Date : 2020-03-26 , DOI: 10.1039/d0qm00073f
David Xi Cao _{1,

2,

3,

4,

5} , Dirk Leifert _{6,

7,

8,

9} , Viktor V. Brus _{1,

2,

3,

4,

5} , Matthew S. Wong _{1,

2,

3,

4,

5} , Hung Phan _{10,

11,

12} , Brett Yurash _{1,

2,

3,

4,

5} , Norbert Koch _{9,

13,

14,

15,

16} , Guillermo C. Bazan _{1,

2,

3,

4,

5} , Thuc-Quyen Nguyen _{1,

2,

3,

4,

5}

Affiliation

Center for Polymers and Organic Solids
Department of Chemistry and Biochemistry
University of California
Santa Barbara
USA
Institute of Organic Chemistry
University of Münster
48149 Münster
Germany
Fulbright University Vietnam
Ho Chi Minh City
Vietnam
Supramolecular Systems, Integrative Research Institute for the Sciences
Department of Physics
Humboldt University
12489 Berlin

The conjugated polyelectrolyte poly[2,6-(4,4-bis-potassium butanylsulfonate-4H-cyclopenta-[2,1-b;3,4-b′]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBTSO₃K, or CPE-K) is part of a unique class of organic semiconducting polymers that are soluble in water and become doped in the presence of a proton source. One of these proton sources is water, which CPE-K is exposed to during purification by dialysis, allowing for its immediate use without an additional doping step. Previous studies have suggested that the actual dopant is H⁺, and that the addition of sodium hydroxide to CPE-K reverses the process and de-dopes the polymer. Curiously, the majority of these water-soluble self-doped polymers in the literature contain a pendant sulfonate group. However, a detailed study to gain insight into the importance of the sulfonate group in water-soluble self-doped polymer systems is lacking, despite its widespread presence in the literature. In this work, using Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible-near infrared (UV-vis-NIR) absorption spectroscopy, we are able to elucidate the role of the pendant sulfonate group with regards to the fundamental doping mechanism of CPE-K. Specifically, we found the CPDT unit can be protonated by water, which is due to both the stabilizing influence of the sulfonate group, and the relatively high oxidation potential of the CPDT unit, both of which are required for self-doped water soluble polymer systems. Furthermore, we estimate the doping efficiency of CPE-K using electrical measurements and X-ray reflectivity (XRR), and reveal several different methods for the doping and de-doping of this material, showcasing this particular material's superior versatility.

中文翻译：

磺酸盐对水溶性共轭聚电解质PCPDTBT-SO3K自掺杂机理的重要性

的共轭聚电解质聚[2,6-（4,4-双-钾butanylsulfonate -4- ħ -cyclopenta- [2,1- b ; 3,4- b ']二噻吩） - ALT -4,7-（2- （1,3-苯并噻二唑）]（PCPDTBTSO ₃ K或CPE-K）是一类独特的有机半导体聚合物的一部分，该聚合物可溶于水并在质子源的存在下被掺杂。这些质子来源之一是水，CPE-K在透析纯化过程中会暴露在水中，无需额外的掺杂步骤即可立即使用。先前的研究表明，实际的掺杂剂是H ⁺并且向CPE-K中添加氢氧化钠会逆转该过程并对聚合物进行去掺杂。奇怪的是，文献中的大多数这些水溶性自掺杂聚合物都含有一个侧基磺酸盐基团。然而，尽管文献中广泛存在磺酸盐基团在水溶性自掺杂聚合物体系中的重要性的深入研究，但缺乏深入的研究。在这项工作中，使用傅立叶变换红外光谱（FTIR），X射线光电子能谱（XPS）和紫外可见近红外（UV-vis-NIR）吸收光谱，我们能够阐明悬垂物的作用关于CPE-K的基本掺杂机理的磺酸盐基团。具体来说，我们发现CPDT单元可以被水质子化，这是由于磺酸根基团的稳定作用，CPDT单元的氧化电位较高，这都是自掺杂水溶性聚合物体系所必需的。此外，我们使用电学测量和X射线反射率（XRR）估算了CPE-K的掺杂效率，并揭示了几种不同的掺杂和去掺杂这种材料的方法，展示了这种特殊材料的卓越多功能性。

更新日期：2020-04-24

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