Reaction Site Designation by Intramolecular Electric Field in Tröger's‐Base‐Derived Conjugated Microporous Polymer for Near‐Unity Selectivity of CO₂ Photoconversion

Abstract To facilitate solar‐driven overall CO₂ and H₂O convsersion into fuels and O₂, a series of covalent microporous polymers derived from Tröger's base are synthesized featuring flexural backbone and unusual charge‐transfer properties. The incorporation of rigid structural twist Tröger's base unit grants the polymers enhanced microporosity and CO₂ adsorption/activation capacity. Density function theory calculations and photo‐electrochemical analyses reveal that an electric dipole moment (from negative to positive) directed to the Tröger's base unit is formed across two obliquely opposed molecular fragments and induces an intramolecular electric field. The Tröger's base unit located at folding point becomes an electron trap to attract photogenerated electrons in the molecular network, which brings about suppression of carrier recombination and designates the reaction site in synergy with the conjugated network. In response to the discrepancy in reaction pathways across the reaction sites, the product allocation in the catalytic reaction is thereby regulated. Optimally, CMP‐nTB achieves the highest photocatalytic CO production of 163.53 µmol g⁻¹ h⁻¹ with approximately unity selectivity, along with H₂O oxidation to O₂ in the absence of any photosensitizer or co‐catalyst. This work provides new insight for developing specialized artificial organic photocatalysts.