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Title: Moderated Basicity of Endohedral Amine Groups in an Octa‐Cationic Self‐Assembled Cage
Abstract

A self‐assembled FeII4L6cage 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 pKaunit 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.

 
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Award ID(s):
2002619 1904577
NSF-PAR ID:
10364097
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie International Edition
Volume:
61
Issue:
11
ISSN:
1433-7851
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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