Monterde Cristina, Pintado-Sierra Mercedes, Navarro Rodrigo, Sánchez Félix, Iglesias Marta
Instituto de Ciencia de Materiales de Madrid, CSIC, C/ Sor Juana Inés de la Cruz, 3, Madrid 28049, Spain.
Instituto de Química Orgánica General, CSIC, C/ Juan de la Cierva, 3, Madrid 28006, Spain.
ACS Appl Mater Interfaces. 2020 Apr 1;12(13):15108-15114. doi: 10.1021/acsami.9b22419. Epub 2020 Mar 19.
This paper reports a simple approach for the preparation of new photo-active conjugated porous polymers (CPPs) based on phenanthrene building blocks with a high Brunauer-Emmett-Teller (BET) surface area. Starting from 2,7-diiodophenanthrene-9,10-dione and its bis-dioxolane derivative with different alkynyl comonomers, we prepared a series of CPPs by C-C Sonogashira-Hagihara coupling activated by microwaves. Moreover, we demonstrated that these functionalized CPPs after hydrolysis to the corresponding diketones show much higher BET surface areas than those obtained directly from the phenanthrene-9,10-dione monomer. Reaction of diketone-hydrolyzed polymers with 2,4-difluoro-6-hydroxybenzaldehyde yields phenantroimidazole derivatives. Indeed, these structurally robust polymers result in efficient, recyclable, heterogeneous photo-organocatalysts for the aza-Henry reaction (C-H functionalization) induced by visible-light irradiation.
本文报道了一种基于菲结构单元制备具有高比表面积的新型光活性共轭多孔聚合物（CPP）的简单方法。以2,7-二碘菲-9,10-二酮及其双二氧戊环衍生物与不同的炔基共聚单体为原料，通过微波活化的C-C Sonogashira-Hagihara偶联反应制备了一系列CPP。此外，我们还证明，这些官能化的CPP水解为相应的二酮后，其比表面积比直接由菲-9,10-二酮单体得到的CPP高得多。二酮水解聚合物与2,4-二氟-6-羟基苯甲醛反应生成菲并咪唑衍生物。实际上，这些结构稳定的聚合物可作为高效、可回收的多相光有机催化剂，用于可见光照射诱导的氮杂-Henry反应（C-H官能化反应）。
