Department of Chemistry, CB#3290, University of North Carolina, Chapel Hill, North Carolina 27599, United States.
J Am Chem Soc. 2011 Feb 23;133(7):2056-9. doi: 10.1021/ja109166b. Epub 2011 Jan 28.
Porous cross-linked polymers (PCPs) with phosphorescent Ru(bpy)(3) and Ir(ppy)(2)(bpy) building blocks were obtained via octacarbonyldicobalt (Co(2)(CO)(8))-catalyzed alkyne trimerization reactions. The resultant Ru- and Ir-PCPs exhibited high porosity with specific surface areas of 1348 and 1547 m(2)/g, respectively. They are thermally stable at up to 350 °C in air and do not dissolve or decompose in all solvents tested, including concentrated hydrochloric acid. The photoactive PCPs were shown to be highly effective, recyclable, and reusable heterogeneous photocatalysts for aza-Henry reactions, α-arylation of bromomalonate, and oxyamination of an aldehyde, with catalytic activities comparable to those of the homogeneous Ru(bpy)(3) and Ir(ppy)(2)(bpy) photocatalysts. This work highlights the potential of developing photoactive PCPs as highly stable, molecularly tunable, and recyclable and reusable heterogeneous photocatalysts for a variety of important organic transformations.
具有磷光 Ru(bpy)(3) 和 Ir(ppy)(2)(bpy) 结构单元的多孔交联聚合物（PCPs）通过八羰基二钴（Co(2)(CO)(8))-催化的炔烃三聚反应获得。所得的 Ru 和 Ir-PCPs 具有高孔隙率，比表面积分别为 1348 和 1547 m(2)/g。它们在空气中高达 350°C 时热稳定，并且在所有测试的溶剂中都不溶解或分解，包括浓盐酸。这些光活性 PCPs 被证明是高效、可回收和可重复使用的非均相光催化剂，可用于 aza-Henry 反应、溴代丙二酸酯的 α-芳基化以及醛的氧化胺化，其催化活性可与均相 Ru(bpy)(3) 和 Ir(ppy)(2)(bpy) 光催化剂相媲美。这项工作突出了开发光活性 PCPs 作为高度稳定、分子可调、可回收和可重复使用的非均相光催化剂的潜力，可用于各种重要的有机转化。
