Effect of Backbone Regiochemistry on Conductivity, Charge Density, and Polaron Structure of n-Doped Donor–Acceptor Polymers
Effect of Backbone Regiochemistry on Conductivity, Charge Density, and Polaron Structure of n-Doped Donor–Acceptor Polymers
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DOI：
10.1021/acs.chemmater.9b00558
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发表时间：
2019-04
影响因子：
8.6
通讯作者：
Suhao Wang;D. Fazzi;Y. Puttisong;M. Jafari;Zhihua Chen;T. Ederth;J. W. Andreasen;Weimin M. Chen;A. Facchetti;S. Fabiano
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文献类型：
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作者：
Suhao Wang;D. Fazzi;Y. Puttisong;M. Jafari;Zhihua Chen;T. Ederth;J. W. Andreasen;Weimin M. Chen;A. Facchetti;S. Fabiano
我们研究了被广泛研究的n掺杂施主-受主聚合物Poly[N，N′-bis(2-octyldodecyl)-1，4，5，8-naphthalenediimide-2，6-diyl]-alt-5，5′-(2，2′-bithiophene)[P(NDI2OD-T2)]中主链区域化学对电导率、电荷密度和极化子结构的影响。与传统的半结晶聚合物如聚(3-己基噻吩基)(P3HT)不同，萘二亚胺(NDI)-联噻吩环(T2)主链的区域不规则(RI)结构并不改变链的分子内空间需求，生成的RI-P(NDI2OD-T2)具有与RR类似的能量学和光学特征。结合电学、UV-Vis/IR、X-射线衍射、电子顺磁共振数据和密度泛函理论计算，定量表征了RR-/RI-P(NDI2OD-T2)的电导率、聚集性、结晶度和电荷密度，并模拟了其极化子结构、分子振动和自旋密度分布。重要的是，我们观察到RI-P(NDI2OD-T2)与其RR对应物相比可以更大程度地掺杂。这一发现是值得注意的，并与基准P3HT形成对比，使我们能够独特地研究区域化学对n掺杂施主-受主聚合物电荷传输特性的作用。
We investigated the influence of backbone regiochemistry on the conductivity, charge density, and polaron structure in the widely studied n-doped donor–acceptor polymer poly[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5′-(2,2′-bithiophene) [P(NDI2OD-T2)]. In contrast to classic semicrystalline polymers such as poly(3-hexylthiophene) (P3HT), the regioirregular (RI) structure of the naphthalenediimide (NDI)-bithiophene (T2) backbone does not alter the intramolecular steric demand of the chain versus the regioregular (RR) polymer, yielding RI-P(NDI2OD-T2) with similar energetics and optical features as its RR counterpart. By combining the electrical, UV–vis/infrared, X-ray diffraction, and electron paramagnetic resonance data and density functional theory calculations, we quantitatively characterized the conductivity, aggregation, crystallinity, and charge density, and simulated the polaron structures, molecular vibrations, and spin density distribution of RR-/RI-P(NDI2OD-T2). Importantly, we observed that RI-P(NDI2OD-T2) can be doped to a greater extent compared to its RR counterpart. This finding is remarkable and contrasts benchmark P3HT, allowing us to uniquely study the role of regiochemistry on the charge-transport properties of n-doped donor–acceptor polymers.