Wiring Covalent Organic Frameworks with Conducting Polymers

Abstract Covalent organic frameworks are a class of crystalline porous polymers formed by linking organic units into periodically aligned skeletons and pores. Here we report a strategy for wiring these frameworks with conducting polymers via wall engineering and polymerization. We anchored each edge site with one pyrrole unit, which is densely packed along the z direction yet protruded from pore walls. This assembly enables the polymerization of pyrrole units to form polypyrrole and creates a new polypyrrole chain conformation. The resultant framework constitutes six single file polypyrrole chains in each pore and develop spatially segregated yet built‐in single molecular wires with exceptional stable polarons. Hall effect measurements revealed that the materials are p ‐type semiconductors, increase conductivity by eight orders of magnitude compared to the pristine frameworks, and achieve a carrier mobility as large as 13.2 cm 2 V −1 s −1 . Our results open an avenue to π electronic frameworks by interlayer molecular wiring with conducting polymers.