Reusable solid fluorination reagents and heterogeneous catalysts are ideally suited for late-stage fluorination with fast and clean conversion and simplified work-up. Here we report Pd-functionalized two-dimensional metal-organic layers (MOLs) as solid reagents and heterogeneous catalysts to efficiently fluorinate a broad scope of aromatic compounds. Site isolation in the MOLs provides a unique opportunity to stabilize highly active F-containing species for the chemical conversion. A terpyridine (TPY)- based ligand on the MOL, together with a 2-chloro-1,10-phenanthroline (phenCl) as a co-ligand, chelates Pd^II to form a reactive center. After treatment with Selectfluor/H₂O, an (N-fluoroxy)-(2-chloro)-phenanthrolinium [N-(FO)-phenCl⁺] moiety is produced from the co-ligand on the Pd center. This active species serves as a stochiometric solid fluorination reagent, which shows different regioselectivities and reactivities as compared to homogeneous catalysts that involves Pd^III/IV-F intermediates in catalytic cycles. The MOLs can also be used as heterogeneous catalysts for fluorination using Selectfluor. This work highlights opportunities in using MOLs to stabilize unique active sites for late-stage fluorination.

可重复使用的固体氟化试剂和非均相催化剂非常适合后期氟化，具有快速，干净的转化率和简化的后处理。在这里，我们报告钯功能化的二维金属有机层（MOL）作为固体试剂和非均相催化剂，以有效地氟化各种芳香族化合物。MOL中的位点隔离提供了独特的机会来稳定高活性的含F物质，以进行化学转化。MOL上的基于三联吡啶（TPY）的配体与2-氯-1,10-菲咯啉（phenCl）作为共配体一起螯合Pd ^II以形成反应中心。用Selectfluor / H ₂ O处理后，（N-氟氧基）-（2-氯）-菲咯啉[N-（FO）-phenCl ⁺]部分由Pd中心上的共配体产生。该活性物质用作化学计量的固体氟化试剂，与在催化循环中涉及Pd ^{III / IV} -F中间体的均相催化剂相比，具有不同的区域选择性和反应性。该MOL还可用作使用Selectfluor进行氟化的非均相催化剂。这项工作突显了使用MOL稳定后期氟化反应独特的活性位点的机会。