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

Jin Ming Wang, Qin Yao Zhu, Jeong Heon Lee, Tae Gyun Woo, Yue Xing Zhang, Woo-Dong Jang and Tae Kyu Kim ()
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Jin Ming Wang: Yonsei University
Qin Yao Zhu: Yonsei University
Jeong Heon Lee: Yonsei University
Tae Gyun Woo: Yonsei University
Yue Xing Zhang: Dezhou University
Woo-Dong Jang: Yonsei University
Tae Kyu Kim: Yonsei University

Nature Communications, 2023, vol. 14, issue 1, 1-13

Abstract: Abstract Diatomic-site catalysts (DACs) garner tremendous attention for selective CO2 photoreduction, especially in the thermodynamical and kinetical mechanism of CO2 to C2+ 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-Ru2DAC and ZnPor-Cu2DAC) present the best CO selectivity. In-situ spectroscopic measurements reveal that the heteronuclear Ru–Cu sites easily appear C1 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 C1 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 C1 intermediates on diatomic sites.

Date: 2023
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DOI: 10.1038/s41467-023-39580-5

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