Robust covalent organic frameworks (COFs) with abundant redox-active sites have attracted intense attention for organic cathode materials due to the ordered structure and excellent stability. Herein, a two-dimensional (2D) crystalline copper-porphyrin covalent triazine framework (CuBCPP-CTF) was synthesized via polycondensation of 5,15-bis(4-cyanophenyl) porphyrin (H₂BCPP) and followed by post-copperization. The integration of copper-porphyrin moieties and triazine linkages provides two kinds of functional sites for outstanding Li⁺ and PF₆⁻ ions storage. Electrochemical studies reveal a high discharge capacity of 232 mAh·g⁻¹ at 200 mA·g⁻¹ and high mid-point voltage (2.77 V vs. Li⁺/Li), corresponding to an outstanding energy density of 601 Wh·kg⁻¹. Density functional theory calculations and ex-situ characterizations disclose the intrinsic bipolar redox mechanism of metalloporphyrin for both PF₆⁻ and Li⁺ accommodation and p-type triazine units for PF₆⁻ storage.

The development of heterogeneous molecule-based catalysts for red light-mediated photocatalysis is still challenging due to the improper light absorption for most materials and the photoactivity deactivation for solid assembly. Herein, red light photocatalysis with a hydrogen-bonded organic framework (HOF) is established. This HOF, named HOF-66, is formed from the self-assembly of guanine-decorated naphthalenediimide (NDI) molecule through hydrogen-bonded guanine-quadruplex nodes, showing square grid supramolecular layers confirmed by powder X-ray diffraction analysis. In contrast to unsubstituted NDI HOF, introduction of ethylamino groups to NDI core in HOF-66 tunes strong electronic maximum absorption peak to 619 nm, allowing red light photocatalysis of singlet oxygen evolution proved by 1,3-diphenylisobenzofuran degradation and electron spin resonance determination. Particularly, under the same conditions, the sulfide oxidation rate in the presence of HOF-66 was 28 times higher compared to its unsubstituted analogue. This work integrates the molecular design and aggregation effect towards the application of HOFs, opening a new gate for red light photocatalysts.