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 Ru4d–Cu3d 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.