可溶液加工交联多孔有机聚合物的迷人面貌

IF 14 Q1 CHEMISTRY, MULTIDISCIPLINARY
Madhurima Sarkar, Suprabhat Sarkar, Monisha Saha, Khushi Luvani, Abhijit Patra
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引用次数: 0

摘要

多孔有机聚合物(POPs)是一种有机网络,具有高度交联结构和内在多孔性。POPs 具有优异的水热稳定性和多样化的应用前景,因此越来越受到重视。然而,传统的金属催化高温反应使用刚性结构单元生成的持久性有机污染物为不溶性粉末状,这给加工成不同形状的器件集成和光电应用带来了挑战。成功制备可溶性多孔有机聚合物有赖于采用特定的设计策略和反应条件来限制分子量和广泛交联。近几十年来,研究人员一直在积极探索各种设计策略,如通过超支化限制分子量和采用受控聚合物生长策略,以生产可溶液加工的无定形多孔有机聚合物。然而,针对特定应用的定向合成方法仍未得到充分发展,因此有必要深入探讨当前可用的策略和未来可能的途径。在此背景下,本报告重点介绍了可溶液加工无定形交联多孔有机聚合物(SCPOPs)领域的进展,阐述了各种设计策略和功能导向型应用。为了应对与非晶交联多孔有机聚合物溶液加工相关的挑战,我们的研究小组专注于微调分子构件之间的非共价相互作用,这是实现多孔聚合物多孔性和可溶性的关键。根据这一原则,我们在单体和共聚单体单元中引入长烷基链作为柔性基团,使其具有高度的旋转自由度和较大的扭转角。这种方法有助于减轻明显的 π-π 堆积相互作用和广泛的交联,从而提高多孔聚合物的溶解度。因此,分析物与 SCPOPs 中带有芳香构建单元的低密度聚合物链之间的便捷相互作用为溶液中基于荧光的硝基芳香族传感提供了可能。此外,荧光多孔聚合物纳米粒子的稳定分散体可以成为一个极具吸引力的平台,用于检测水中的分析物,并提高灵敏度。荧光 SCPOPs 的多孔性使其能够封装不同的染料分子,而控制从聚合物到染料的能量传递效率可实现荧光调节,从而在溶液、纳米颗粒、凝胶和透明薄膜中发射白光。此外,我们还证明了在交联聚合物中加入交替的供体-受体单元可为光驱动的氧化还原反应(如苄胺的光氧化反应和氢进化反应)带来最佳带位。我们研究了一种采用溶液可加工持久性有机污染物的双相催化路线,以提高效率,同时促进光催化剂的回收和再利用。正如本综述所详述的,对 SCPOPs 的设计策略和潜在应用的全面考察,为深入研究设计新型可加工功能多孔材料铺平了道路,满足了当前可持续发展目标的需要。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Intriguing Facets of Solution Processable Cross-Linked Porous Organic Polymers

Intriguing Facets of Solution Processable Cross-Linked Porous Organic Polymers
Porous organic polymers (POPs) are organic networks distinguished by their highly cross-linked structures and their intrinsic porosity. The growing emphasis on POPs is driven by their exceptional hydrothermal stability and diverse application prospects. However, traditional metal-catalyzed high-temperature reactions using rigid building units yield POPs in insoluble powder form, posing challenges for processing into different shapes for device integration and optoelectronic applications. The successful fabrication of a soluble porous organic polymer relies on the employment of specific design strategies and reaction conditions to restrict the molecular weight and extensive cross-linking. In recent decades, researchers have been actively exploring various design strategies, such as limiting molecular weight through hyperbranching and employing controlled polymer growth strategies, to produce solution processable amorphous porous organic polymers. However, targeted synthesis for specific applications remains underdeveloped, justifying the need for an in-depth deliberation of currently available strategies and possible future avenues. In this context, this Account highlights the advancements in the field of solution processable amorphous cross-linked porous organic polymers (SCPOPs), describing diverse design strategies and function-led applications. In order to address the challenges associated with the solution processing of amorphous cross-linked POPs, our research group has focused on fine-tuning the noncovalent interactions among the molecular building blocks, the key to achieving both porosity and solubility in the resultant porous polymer. Following this principle, we introduce long alkyl chains as flexible groups in the monomer and comonomer units that offer a high degree of rotational freedom and a substantial twist angle. This approach facilitates alleviation of the pronounced π–π stacking interaction and extensive cross-linking, thereby enhancing the solubility of the porous polymer. As a result, the facile interaction between the analytes and inefficiently packed polymer chains with aromatic building units in SCPOPs opens the scope for fluorescence-based nitroaromatic sensing in solution. Further, a stable dispersion of fluorescent porous polymer nanoparticles could be an attractive platform for analyte detection in water with enhanced sensitivity. The porous nature of the fluorescent SCPOPs enables the encapsulation of diverse dye molecules, and controlling the energy transfer efficiency from polymer to dyes results in fluorescence tuning, leading to the emission of white light in solution, nanoparticles, gel, and a thin transparent film. Furthermore, we demonstrate that incorporating alternate donor–acceptor units into the cross-linked polymer leads to the optimum band positions for light-driven redox reactions, such as photooxidation of benzylamine and hydrogen evolution. We investigated a biphasic catalysis route employing solution-processable POPs to enhance the efficiency while facilitating the recovery and reusability of the photocatalysts. As detailed in this review, the comprehensive inspection of the design strategies and potential applications of SCPOPs paves the way to delve into designing new processable functional porous materials, catering to the need for current sustainable development goals.
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