Cooperative Thermodynamic Control of Selectivity in the Self-Assembly of Rare Earth Metal鈥揕igand Helices

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• 作者：Amber M. Johnson ; Michael C. Young ; Xing Zhang ; Ryan R. Julian ; Richard J. Hooley
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：November 27, 2013
• 年：2013
• 卷：135
• 期：47
• 页码：17723-17726
• 全文大小：311K
• 年卷期：v.135,no.47(November 27, 2013)
• ISSN：1520-5126

文摘

Metal-selective self-assembly with rare-earth cations is possible with suitable rigid, symmetrical bis-tridentate ligands. Kinetically controlled formation is initially observed, with smaller cations preferentially incorporated. Over time, the more thermodynamically favorable complexes with larger metals are formed. This thermodynamic control is a cooperative supramolecular phenomenon and only occurs upon multiple-metal-based self-assembly: single-metal ML₃ analogues do not show reversible selectivity. The selectivity is dependent on small variations in lanthanide ionic radius and occurs despite identical coordination-ligand coordination geometries and minor size differences in the rare-earth metals.