Easily Switchable 18π‐, 19π‐, and 20π‐Conjugation of Diazaporphyrin Double‐Pincer Bispalladium Complexes
Easily Switchable 18π‐, 19π‐, and 20π‐Conjugation of Diazaporphyrin Double‐Pincer Bispalladium Complexes
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轻松切换二氮杂卟啉双钳双钯配合物的 18π、19π 和 20π 共轭
DOI：
10.1002/anie.202300437
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Shinokubo Hiroshi
中科院分区：
文献类型：
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作者：
Sakurai Takahiro;Hiraoka Yuya;Tanaka Hisaaki;Miyake Yoshihiro;Fukui Norihito;Shinokubo Hiroshi
NiII3,7,13,17-四吡啶基-5,15-二氮杂卟啉作为 PdII 离子的双三齿配体，提供钳型双钯配合物。电化学分析表明，由于两个阳离子 PdII 中心与氮原子的配位，双钯配合物表现出优异的接受电子能力和可逆氧化还原性能。我们分离并表征了双钯配合物的单电子和双电子还原物质。双电子还原物质的 20π 反芳香性质通过 1 H NMR 光谱、紫外/可见近红外 (NIR) 吸收光谱和密度泛函理论 (DFT) 计算得到证实。 X 射线衍射揭示了双钯配合物的高度扭曲结构，无论氧化态如何。
NiII3,7,13,17‐tetrapyridyl‐5,15‐diazaporphyrin serves as a double tridentate ligand to PdIIions to provide a pincer‐type bispalladium complex. Electrochemical analysis revealed that the bispalladium complex shows excellent ability to accept electrons and reversible redox properties due to the coordination of the two cationic PdIIcenters to themeso‐nitrogen atoms. We isolated and characterized one‐ and two‐electron reduction species of the bispalladium complex. The 20π antiaromatic nature of the two‐electron reduction species was confirmed by1H NMR spectroscopy, UV/Vis‐near‐IR (NIR) absorption spectra, and density functional theory (DFT) calculations. X‐ray diffraction revealed highly twisted structures for the bispalladium complexes regardless of the oxidation state.