Moderated Basicity of Endohedral Amine Groups in an Octa‐Cationic Self‐Assembled Cage. Issue 11 (27th January 2022)

• Record Type: Journal Article
• Authors: Ngai, Courtney; Wu, Hoi‐Ting; da Camara, Bryce; Williams, Christopher G.; Mueller, Leonard J.; Julian, Ryan R.; Hooley, Richard J.
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 11(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-27
• Subjects: Supramolecular Chemistry -- Self-Assembly -- Coordination Chemistry -- Enzyme Models -- Molecular Recognition; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202117011
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A self‐assembled Fe II 4 L6 cage was synthesized with 12 internal amines in the cavity. The cage forms as the dodeca‐ammonium salt, despite the cage carrying an overall 8+ charge at the metal centers, extracting protons from displaced water in the reaction. Despite this, the basicity of the internal amines is lower than their counterparts in free solution. The 12 amines have a sliding scale of basicity, with a ≈6 p K a unit difference between the first and last protons to be removed. This moderation of side‐chain basicity in an active site is a hallmark of enzymatic catalysis. Abstract : An endohedrally functionalized self‐assembled Fe4 L6 cage complex with 12 internal amines in the cavity acts as an acid host, and shows differential basicity, moderated by the cage superstructure.