Solution Conformation and Self-Assembly of Ferrocenyl(thio)ureas

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• 作者：Kristina Hanauer ; Minh Thu Pham ; Christoph Fö ; rster and Katja Heinze
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2017
• 出版时间：January 10, 2017
• 年：2017
• 卷：2017
• 期：2
• 页码：433-445
• 全文大小：2484K
• ISSN：1099-0682c

文摘

Conformations and (dis)assembly processes of ureas and thioureas are of fundamental importance in supramolecular chemistry, anion binding, or crystal engineering, both in solution and in the solid state. For sensing and switching processes a redox-active unit, such as the ferrocene/ferrocenium couple, is especially suitable. Here, self-assembly processes of redox-active ferrocenyl(thio)ureas FcNHC(X)NHR [X = O, R = Fc (1), Ph (2), 1-naphthyl (3), Me (4), Et (5); X = S, R = Fc (6), 1-anthracenyl (7)] through hydrogen bonds – both in the solid state and in THF and CH₂Cl₂ solution – are reported. Special emphasis is placed on the impact of nonclassical intramolecular NH···Fe hydrogen bonds in these organometallic systems [these are absent in conventional organic (thio)ureas] on conformation and assembly. Furthermore, conformational switching and disassembly of 1–6 is induced by oxidation of 1–6 to the corresponding ferrocenium cations 1⁺–6⁺ (redox switch).