The redox state of the phthalocyanine in sandwich lanthanide complexes is crucial for their applications. In this work, we demonstrate that the cation-induced supramolecular assembly of crown-substituted phthalocyanine lanthanide complexes Ln[(15C5)₄Pc]₂ can be used to control the redox state of the ligand simultaneously with the coordination sphere of the central metal. We achieve unprecedented redox switching of phthalocyanine ligands in a double-decker Gd(III) complex, resulting from the intramolecular inclusion of potassium cations between the decks with simultaneous twisting of the ligands (the skew angle between them decreases from 44.61 to 0.21°). Such a structural change leads to an increase in the deck-to-deck distance and drastically facilitates ligand reduction. This process was shown to be anion-dependent: only potassium salts of weak acids (KOPiv and KOAc) induce intramolecular inclusion of cations with redox switching in contrast to salts of strong acids (KBr, KOPic, KSCN, and KPF₆), where such a redox process does not occur. This breakthrough opens new avenues for controlling the electrochromic properties, of phthalocyanines, along with other properties, such as electrical conductivity, optics, etc.

中文翻译：

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三明治 Gd 双酞菁酸盐中意外的超分子诱导氧化还原转换

夹心稀土配合物中酞菁的氧化还原态对其应用至关重要。在这项工作中，我们证明了冠取代酞菁镧系配合物Ln[(15C5) ₄ Pc] ₂的阳离子诱导超分子组装可用于同时控制配体的氧化还原态和中心金属的配位球。我们在双层 Gd(III) 配合物中实现了前所未有的酞菁配体氧化还原转换，这是由于在配体之间分子内包含钾阳离子并同时扭转配体（它们之间的倾斜角从 44.61 减小到 0.21°）。这种结构变化导致甲板间距离增加，并极大地促进配体减少。该过程被证明是阴离子依赖性的：与强酸的盐（KBr、KOPic、KSCN 和 KPF ₆）相比，只有弱酸的钾盐（KOPiv 和 KOAc）会诱导分子内包含具有氧化还原转换的阳离子，其中此类不发生氧化还原过程。这一突破为控制酞菁的电致变色特性以及其他特性（如导电性、光学等）开辟了新途径。