Strong Proton-Electron Coupling in π‐Planar Metal Complex with Redox‐Active Ligands
Strong Proton-Electron Coupling in π‐Planar Metal Complex with Redox‐Active Ligands
复制标题
具有氧化还原活性配体的 π 平面金属配合物中的强质子-电子耦合
DOI：
10.1002/anie.202204521
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Kitagawa Hiroshi
中科院分区：
文献类型：
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作者：
Huang Pingping;Yoshida Yukihiro;Nakano Yoshiaki;Yamochi Hideki;Hayashi Mikihiro;Kitagawa Hiroshi
金属配合物的质子耦合电子转移（PCET）已被广泛研究，特别是在生物化学和催化化学中。尽管带有氧化还原活性配体的金属配合物在这些研究领域中发挥了作用，但那些具有π平面结构的金属配合物仍然完全未被探索，这对离子电子学的未来发展至关重要。本文采用实验和理论相结合的方法，研究了一种含有氧化还原活性N，S-配体的π平面镍配合物Ni（itsq）2的质子-电子耦合.强的质子-电子耦合表现在大的电位偏移中，其是具有氧化还原非活性配体的典型PCET-型π-平面金属络合物[Ni（dcpdt）2]2-的两倍。理论计算证实，质子化对前线轨道的稳定作用在Ni（itsq）2中比在[Ni（dcpdt）2]2−中更大。这些结果表明，具有氧化还原活性配体的π-平面金属配合物有希望用于开发新型PCET-型材料。
Proton‐coupled electron transfer (PCET) of metal complexes has been widely studied, especially in biochemistry and catalytic chemistry. Although metal complexes bearing redox‐active ligands play a part in these research areas, those with π‐planar structure remain entirely unexplored, which are vital for future development of iono‐electronics. Here, proton‐electron coupling of a π‐planar nickel complex bearing redox‐active N,S‐ligands, Ni(itsq)2, was investigated by combining experimental and theoretical approaches. Strong proton‐electron coupling was manifested in a large potential shift, which is twice greater than that of a typical PCET‐type π‐planar metal complex with redox‐inactive ligands, [Ni(dcpdt)2]2−. Theoretical calculations affirmed that the stabilization of frontier orbitals by protonation is greater in Ni(itsq)2than that in [Ni(dcpdt)2]2−. These results indicate that π‐planar metal complexes with redox‐active ligands are promising for developing novel PCET‐type materials.