Starfish‐Inspired Flexible Conductive Ester‐Linked Porphyrin Covalent Organic Framework With “Corrugated Mesh” Stacking Conformer for High Performance Electrochemical Ion Storage

ABSTRACT

The dynamic adaptability of flexible covalent organic frameworks (COFs) offers unique opportunities for advanced electrochemical systems. However, flexible nonconjugated linkers disrupt long‐range charge delocalization, making it challenging to reconcile framework high conductivity with flexibility. Here, inspired by starfish's skeletal conformer adaptive maintenance, we proposed a stacking conformer orchestration biomimetic strategy to construct a flexible conductive ester‐linked porphyrin COF (Ester‐THP‐COF) featuring starfish‐like skeletal “corrugated mesh” stacking conformer. Twisting modulation of the C─O─C dihedral angle locks adjacent layers into an AA‐eclipsed conformer, suppressing interlayer slippage to achieve anisotropic charge transport. The resulting Ester‐THP‐COF exhibited the highest electrical conductivity among the flexible COFs, reaching 6.8 × 10 ⁻³ S·cm ⁻¹ . Meanwhile, flexible ester linkages impart pronounced ion‐embedding adaptability. The Ester‐THP‐COF electrode achieves a record‐breaking Na ⁺ storage capacity of 62.5 mg g ⁻¹ , while maintaining self‐reinforcing capacity stability of 102.8%–107.9% within large hydration size ionic systems (spanning Na ⁺ to Ca ²⁺ /Mg ²⁺ ). In‐situ characterizations revealed that hydrated‐ion insertion induces adaptive lattice respiration, progressively exposing buried interlayer porphyrin sites and enabling rapid, reversible ion coordination. This work establishes a molecular‐level design principle for integrating high conductivity and flexibility in COFs, advancing adaptive reticular porous materials for next‐generation electrochemical applications.