Dual-Spin Centers in a Grid-like Covalent Organic Framework Promote Near-Unity CO₂ Electroreduction

Spin manipulation has emerged as a promising strategy for enhancing molecular electrocatalytic performance. However, precisely controlling dual spin centers and delineating their contribution to reaction kinetics remain a considerable challenge. Herein, we demonstrate that incorporating quinone moieties into a grid-like covalent organic framework (COF) enables a dual-spin-center catalysis system, simultaneously stabilizing semiquinone radicals and inducing an electronic reconfiguration with low-spin character at the cobalt center. Spectroscopic and theoretical analyses reveal a synergistic mechanism. The spin-polarized electron density of semiquinone radicals creates an internal potential gradient that promotes electron transfer, while their favorable π-π interactions enhance CO₂ affinity and boost CO₂ activation efficiency. Meanwhile, the cobalt site with a computed e_g¹ occupancy (low-spin) leads to more delocalized d-electrons, a downshifted d-band center, and optimized intermediate adsorption. As a result, the dual-spin system achieves reduced barriers for *COOH formation via spin-coupling interactions and facilitated *CO desorption, collectively enabling near-unity selectivity for CO₂-to-CO conversion. This work establishes the concurrent engineering of organic and metal spin environments as a foundational design principle for advanced molecular electrocatalysts.