Moderated Basicity of Endohedral Amine Groups in an Octa‐Cationic Self‐Assembled Cage
Courtney Ngai, Hoi‐Ting Wu, Bryce da Camara, Christopher G. Williams, Leonard J. Mueller, Ryan R. Julian, Richard J. Hooley
Abstract
Abstract A self‐assembled Fe II 4 L 6 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.
Topics & Concepts
CageCationic polymerizationChemistryAmine gas treatingAmmoniumCatalysisSalt (chemistry)Inorganic chemistryPolymer chemistryMedicinal chemistryPhotochemistryOrganic chemistryCombinatoricsMathematicsSupramolecular Chemistry and ComplexesDNA and Nucleic Acid ChemistryPorphyrin and Phthalocyanine Chemistry