Impact of Molecular Design on Degradation Lifetimes of Degradable Imine-Based Semiconducting Polymers
Impact of Molecular Design on Degradation Lifetimes of Degradable Imine-Based Semiconducting Polymers
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DOI：
10.1021/jacs.1c12845
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发表时间：
2022-03-02
影响因子：
15
通讯作者：
Bao, Zhenan
中科院分区：
文献类型：
--
作者：
Chiong, Jerika A.;Zheng, Yu;Bao, Zhenan
瞬态电子学由于其在环境和人类健康方面的潜在应用而成为一个迅速兴起的领域。最近，一些研究已经将酸不稳定的亚胺键纳入聚合物半导体中以赋予瞬时性;然而，对这些聚合物的结构-降解性质关系的理解是有限的。在这项研究中，我们系统地设计和表征了一系列完全可降解的二酮基吡咯并吡咯基聚合物与工程侧链，研究几个分子设计参数对这些聚合物的降解寿命的影响。通过监测降解动力学，通过紫外-可见光谱，我们发现，聚合物在溶液中的降解是聚集依赖的基础上的分支点和M-n，加速降解速率促进减少聚集。另外，增加聚合物的亲水性促进水扩散，并因此促进亚胺键沿着聚合物主链的酸水解。这些聚合物的聚集特性和降解寿命在很大程度上依赖于溶剂，氯苯中的聚合物降解时间是氯仿中的六倍。我们开发了一种新方法来量化薄膜中聚合物的降解，并观察到类似的因素和考虑因素（例如，链间顺序、微晶尺寸和亲水性）影响亚胺基聚合物半导体的降解。我们发现，三元共聚物作为一个有吸引力的方法，实现可降解的半导体具有良好的电荷传输和调谐降解性能。这项研究为可降解半导体聚合物的分子设计提供了关键原则，我们预计这些发现将加快瞬态电子器件的发展，并具有可控的寿命。
Transient electronics are a rapidly emerging field due to their potential applications in the environment and human health. Recently, a few studies have incorporated acid-labile imine bonds into polymer semiconductors to impart transience; however, understanding of the structure-degradation property relationships of these polymers is limited. In this study, we systematically design and characterize a series of fully degradable diketopyrrolopyrrole-based polymers with engineered sidechains to investigate the impact of several molecular design parameters on the degradation lifetimes of these polymers. By monitoring degradation kinetics via ultraviolet-visible spectroscopy, we reveal that polymer degradation in solution is aggregation-dependent based on the branching point and M-n, with accelerated degradation rates facilitated by decreasing aggregation. Additionally, increasing the hydrophilicity of the polymers promotes water diffusion and therefore acid hydrolysis of the imine bonds along the polymer backbone. The aggregation properties and degradation lifetimes of these polymers rely heavily on solvent, with polymers in chlorobenzene taking six times as long to degrade as in chloroform. We develop a new method for quantifying the degradation of polymers in the thin film and observe that similar factors and considerations (e.g., interchain order, crystallite size, and hydrophilicity) used for designing high-performance semiconductors impact the degradation of imine-based polymer semiconductors. We found that terpolymerization serves as an attractive approach for achieving degradable semiconductors with both good charge transport and tuned degradation properties. This study provides crucial principles for the molecular design of degradable semiconducting polymers, and we anticipate that these findings will expedite progress toward transient electronics with controlled lifetimes.