The ability of light to change the properties of light‐responsive polymers opens avenues for targeted release of cargo with a high degree of spatial and temporal control. Recently, we established photoacid polymers as light‐switchable macromolecular amphiphiles. In these systems, light‐induced excited‐state proton transfer (ESPT) causes changes in amphilicity. However, as the intermolecular process itself critically depends on the local environment of the photoacid unit within the polymer, the overall amphiphilicity directly influences ESPT. Thus, understanding the impact of the local environment on the photophysics of photoacidic side chains is key to material design. In this contribution we address both thermodynamic and kinetic aspects of ESPT in oxazoline‐based amphiphilic polymers with pyrenol‐based photoacid side chains. We will compare the effect of polymer design, i.e. statistical and block arrangements, i.e. in poly[(2‐ethyl‐2‐oxazoline)‐co‐(1‐(6/8‐hydroxyperene)sulphonylaziridine)] and poly(2‐ethyl‐2‐oxazoline)‐block‐poly[(2‐ethyl‐2‐oxazoline)‐co‐(2‐(3‐(6‐hydroxypyrene)sulphona mide)propyl‐2‐oxazoline), on the intermolecular proton transfer reaction by combining steady‐state and time‐resolved absorption and emission spectroscopy. ESPT appears more prominent in the statistical copolymer compared to a block copolymer with overall similar pyrenol loading. We hypothesize that the difference is due to different local chain arrangements adopted by the polymers in the two cases.

中文翻译：

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聚（2-恶唑啉）两亲性调节基于芘醇的聚光酸的激发态质子转移

光改变光响应聚合物特性的能力为高度空间和时间控制的货物定向释放开辟了途径。最近，我们建立了光酸聚合物作为光可切换的高分子两亲物。在这些系统中，光诱导激发态质子转移（ESPT）会导致两亲性发生变化。然而，由于分子间过程本身很大程度上取决于聚合物内光酸单元的局部环境，因此整体两亲性直接影响ESPT。因此，了解当地环境对光酸侧链光物理的影响是材料设计的关键。在这篇文章中，我们解决了具有基于芘醇的光酸侧链的基于恶唑啉的两亲性聚合物中 ESPT 的热力学和动力学方面的问题。我们将比较聚合物设计的效果，即统计和嵌段排列，即聚[(2-乙基-2-恶唑啉)-co-(1-(6/8-羟基苝)磺酰基氮丙啶)]和聚(2-乙基‐2-恶唑啉)-嵌段-聚[(2-乙基-2-恶唑啉)-co-(2-(3-(6-羟基芘)磺酰胺)丙基-2-恶唑啉)，通过分子间质子转移反应结合稳态和时间分辨吸收和发射光谱。与具有总体相似芘醇负载量的嵌段共聚物相比，ESPT 在统计共聚物中显得更为突出。我们假设这种差异是由于两种情况下聚合物采用不同的局部链排列所致。