Spin Alignment in Cr–W–Cr Motif Promotes <i>N</i> , <i>N</i> -Dimethylformamide Electrosynthesis from Dimethylamine Self-Coupling

Formamides are indispensable building blocks in pharmaceuticals and fine chemicals, yet their sustainable synthesis remains challenging. Herein, we present the first electrochemical strategy for the direct synthesis of <i>N</i>,<i>N</i>-dimethylformamide (DMF) via dimethylamine (DMA) self-coupling, eliminating the need of external carbon sources. The designed Cr₂WO₆ catalyst features a Cr-W-Cr motif, where the Cr sites can exhibit either positive and negative spin moments. This spin arrangement creates a spin relay active center that promotes spin-matched C-N coupling between *N(CH₃)₂ and *CHO intermediates, lowing the reaction energy barrier. Notably, with a DMA concentration of 0.1 M, the system delivers a DMF Faradaic efficiency of 45.0% and a yield rate of 21.3 μmol cm^-2 h^-1. At 0.5 M DMA, the yield rate further increases to 60.0 μmol cm^-2 h^-1. This work opens a sustainable and efficient route for DMF production and highlights spin alignment as a design principle for electrochemical C-N bond formation.