Controlling the Complexity and Interconversion Mechanisms in Self‐Assembled [Fe2L3]4+ Helicates and [Fe4L6]8+ Cages. Issue 7 (26th December 2021)

• Record Type: Journal Article
• Authors: Siddique, Rashid G.; Arachchige, Kasun S. A.; AL‐Fayaad, Hydar A.; Thoburn, John D.; McMurtrie, John C.; Clegg, Jack K.
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 7(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-12-26
• Subjects: Kinetics -- Metal-organic cages -- Self-assembly -- Self-sorting -- Systems chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202115555
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Self‐assembled coordination cages and metal–organic frameworks have relied extensively on symmetric ligands in their formation. Here we have prepared a relatively simple system employing an unsymmetric ligand that results in two distinct self‐assembled structures, a [Fe2 L 3 ] 4+ helicate and a [Fe4 L 6 ] 8+ cage composed of 10 interconverting diastereomers and their enantiomers. We show that the steric profile of the ligand controls the complexity, thermodynamics and kinetics of interconversion of the system. Abstract : A dynamic system of interconverting helicates and cages was prepared and characterized. The presence of steric bulk on the central ring of the ligand was found to control both the complexity and interconversion mechanism.