The construction of conjugated covalent organic frameworks (COFs) with strong C–C bond linkage remains a big challenge. Herein, we report a new strategy by using an oxidative C–C coupling reaction between electron-rich pyrrole rings at a liquid–liquid interface. Two threefold symmetric monomers containing three terminal pyrrole units were tested, and both gave two-dimensional conjugated COF films with good crystallinity. The bipyrrole units in the as-formed COFs are partially doped, which can be reduced to the neutral form by hydrazine and redoped by I₂ vapor. The I₂-doped films showed high conductivity (1.35 S/m). Meanwhile, the unpaired electrons exhibited moderate interlayer antiferromagnetic coupling.

具有牢固的C–C键连接的共轭共价有机骨架（COF）的构建仍然是一个巨大的挑战。在这里，我们通过在液-液界面处的富电子吡咯环之间使用氧化性C-C偶联反应来报告一种新的策略。测试了包含三个末端吡咯单元的两个三重对称单体，均得到了具有良好结晶度的二维共轭COF膜。形成的COF中的双吡咯单元是部分掺杂的，可以通过肼还原为中性形式，并通过I ₂蒸汽重掺杂。掺杂有I _2的膜显示出高电导率（1.35 S / m）。同时，未成对的电子表现出中等的层间反铁磁耦合。