Designing new materials for effective detoxification of chemical warfare agents (CWAs) is of current interest given the recent use of CWAs. Although halogenated boron-dipyrromethene derivatives (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene or BDP or BODIPY) at the 2 and 6 positions have been extensively explored as efficient photosensitizers for generating singlet oxygen (1O2) in homogenous media, their utilization in the design of porous organic polymers (POPs) has remained elusive due to the difficulty of controlling polymerization processes through cross-coupling synthetic pathways. Our approach to overcome these difficulties and prepare halogenated BODIPY-based porous organic polymers (X-BDP-POP where X = Br or I) represents an attractive alternative through post-synthetic modification (PSM) of the parent hydrogenated-polymer. Upon synthesis of both the parent polymer, H-BDP-POP, and its post-synthetically modified derivatives, Br-BDP-POP and I-BDP-POP, the BET surface areas of all POPs have been measured and found to be 640, 430, and 400 m2·g-1, respectively. In addition, the insertion of heavy halogen atoms at the 2 and 6 positions of the BODIPY unit leads to quenching of fluorescence (both polymer and solution-phase monomer forms) and enhancement of phosphorescence (detectable for polymer form only), as a result of efficient intersystem crossing. The heterogeneous photocatalytic activities of both the parent POP and its derivative for the detoxification of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), have been examined; the results show significant enhancement in the generation of the singlet oxygen (1O2). Both bromination and iodination of H-BDP-POP served to shorten by five-fold the time needed for selective and catalytic photo-oxidation of CEES to 2-chloroethyl ethyl sulfoxide (CEESO).

中文翻译：

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基于 BODIPY 的多孔有机聚合物 (POPs) 用于硫芥模拟物的光化学解毒

鉴于最近使用 CWA，设计用于有效解毒化学战剂 (CWA) 的新材料是当前的兴趣所在。尽管 2 位和 6 位的卤化硼-二吡咯亚甲基衍生物（4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 或 BDP 或 BODIPY）已被广泛探索作为产生单线态氧 (1O2 ) 在均质介质中，由于难以通过交叉偶联合成途径控制聚合过程，因此它们在多孔有机聚合物 (POP) 设计中的应用仍然难以捉摸。我们克服这些困难并制备基于卤化 BODIPY 的多孔有机聚合物（X-BDP-POP，其中 X = Br 或 I）的方法代表了通过母体氢化聚合物的合成后改性 (PSM) 的有吸引力的替代方案。在合成母体聚合物 H-BDP-POP 及其合成后改性衍生物 Br-BDP-POP 和 I-BDP-POP 后，所有 POPs 的 BET 表面积均已测量并发现为 640，分别为 430 和 400 m2·g-1。此外，在 BODIPY 单元的 2 和 6 位插入重卤原子导致荧光猝灭（聚合物和溶液相单体形式）和磷光增强（仅可检测到聚合物形式），这是由于高效的系统间交叉。已检验母体 POP 及其衍生物对硫芥模拟物 2-氯乙基乙基硫醚 (CEES) 解毒的非均相光催化活性；结果显示单线态氧 (1O2) 的生成显着增强。