Synergistic Co–N/O Coordination and Covalent Grafting Construct Robust Electron–Ion Highways across the CMP-SWCNT Heterointerface

The structural disorder of conjugated microporous polymers (CMPs) presents a trade-off among electrical conductivity, ion transport dynamics, and the efficient utilization of active sites. Here, we present a multiscale engineering strategy that employs M-N x coordination-induced d-π orbital hybridization coupled with covalent interfacial grafting to synergistically reconstruct efficient electron pathways and enhance intrinsic conductivity. The introduction of hierarchical pores facilitates rapid ion permeation and shortens diffusion distances, effectively mitigating sluggish ion kinetics. A brominated salicyl-cyclohexanediamine ligand was designed to coordinate with Co 2+, forming a stable Co–N 2 O 2 tetradentate structure. The cobalt coordination unit was connected with an electron-rich triazine-alkyne monomer via a Sonogashira–Hagihara coupling, yielding a locally ordered conjugated framework. Subsequently, a stable core–shell-like tubular heterostructure was fabricated by covalently grafting CMPs onto carbon nanotubes via in situ interfacial polymerization. The resulting extended π-delocalization lowers charge-transfer barriers, and the synergistic coupling between Co d-orbitals and the π-backbone promotes enhanced electronic delocalization, thereby collectively optimizing the electron transport pathway. This work demonstrates that precise cobalt coordination combined with covalent grafting effectively overcomes the intrinsic limitations of CMPs in conductivity, active-site accessibility, and interfacial ion kinetics, offering a universal and scalable pathway for designing organic–inorganic hybrid electrodes.