Asymmetric gradient orbital interaction of hetero-diatomic active sites for promoting C − C coupling

Diatomic-site catalysts (DACs) garner tremendous attention for selective CO 2 photoreduction, especially in the thermodynamical and kinetical mechanism of CO 2 to C 2+ products. Herein, we first engineer a novel Zn-porphyrin/RuCu-pincer complex DAC (ZnPor-RuCuDAC). The heteronuclear ZnPor-RuCuDAC exhibits the best acetate selectivity (95.1%), while the homoatomic counterparts (ZnPor-Ru 2 DAC and ZnPor-Cu 2 DAC) present the best CO selectivity. In-situ spectroscopic measurements reveal that the heteronuclear Ru–Cu sites easily appear C 1 intermediate coupling. The in-depth analyses confirm that due to the strong gradient orbital coupling of Ru4 d –Cu3 d resonance, two formed * CO intermediates of Ru–Cu heteroatom show a significantly weaker electrostatic repulsion for an asymmetric charge distribution, which result from a side-to-side absorption and narrow dihedral angle distortion. Moreover, the strongly overlapped Ru/Cu- d and CO molecular orbitals split into bonding and antibonding orbitals easily, resulting in decreasing energy splitting levels of C 1 intermediates. These results collectively augment the collision probability of the two * CO intermediates on heteronuclear DACs. This work first provides a crucial perspective on the symmetry-forbidden coupling mechanism of C 1 intermediates on diatomic sites.