Domokos Andras, Aronow Sean D, Tang Teresa, Shevchenko Nikolay E, Tantillo Dean J, Dudnik Alexander S
Department of Chemistry, University of California, Davis, California 95616, United States.
ACS Omega. 2019 May 30;4(5):9427-9433. doi: 10.1021/acsomega.9b01125. eCollection 2019 May 31.
The introduction of functional groups with varying electron-donating/-withdrawing properties at the β-position of diketopyrrolopyrrole (DPP) has been shown to affect the optoelectronic properties of the polymers. We report the synthesis of a new diketopyrrolopyrrole monomer wherein a strong electron-donating substituent, a methoxy group, was incorporated at the β-position in an effort to modulate polymer properties. Homopolymers and co-polymers of the new β-methoxy DPP and nonderivatized DPP were synthesized, and their properties were measured by cyclic voltammetry and UV-vis-near-infrared. Density functional theory computations also were employed to predict the degree of planarity of β-methoxy oligomers to probe the significance of the newly introduced S-O conformational lock. The combined experimental and computational results showed a reduction in the gap between highest occupied molecular orbital/lowest unoccupied molecular orbital levels, a redshift toward the near-infrared region, and an increased planarity in the β-methoxy polymers.
在二酮吡咯并吡咯（DPP）的β位引入具有不同给电子/吸电子性质的官能团已被证明会影响聚合物的光电性能。我们报道了一种新的二酮吡咯并吡咯单体的合成，其中在β位引入了一个强给电子取代基甲氧基，以调控聚合物性能。合成了新型β-甲氧基DPP的均聚物和共聚物以及未衍生化的DPP，并通过循环伏安法和紫外-可见-近红外光谱对其性能进行了测定。还采用密度泛函理论计算来预测β-甲氧基低聚物的平面度，以探究新引入的S-O构象锁的重要性。实验和计算结果相结合表明，最高占据分子轨道/最低未占据分子轨道能级之间的能隙减小，向近红外区域红移，且β-甲氧基聚合物的平面度增加。
