On the Structural Adaptability and Dynamics of Metal-Organic Cages
type: CreativeWork
description: Metal-organic cages are molecular receptors that enable selective molecular recognition and catalysis, yet most current cage systems employ rigid building blocks that limit guest accommodation and environmental adaptability. Developing cages that combine structural integrity with conformational adaptability remains challenging, requiring balance between pre-organisation for discrete assembly and flexibility for responsive behaviour. This thesis explores dynamic and adaptive metal-organic cage systems through strategic incorporation of flexible subcomponents. Three approaches demonstrate how adaptive self-assembly, dynamic structures, and structural transformations enhance supramolecular host functionality. The first approach introduces a conformationally adaptable ZnII₈L₆ pseudo-cubic cage with tetramine subcomponents featuring 2,6-naphthylene rotary units. These enable independent face switching between endo and exo conformations, dynamically expanding cavity volume to accommodate guests ranging from 46 to 154% of the initial cavity size. The system exemplifies Koshland's induced-fit model, demonstrating synthetic assemblies can mimic biological macromolecule adaptability while maintaining structural integrity. The second approach extends this adaptability to the self-assembly of heteroleptic cages, using the same adaptive tetramine to match triangular building blocks of increasing size. This generates three distinct ZnII₆L₃L'₂ triangular prismatic cages with conformations from near-equilateral to elongated geometries. The 2,6-naphthylene units provide geometric flexibility enabling adaptive matching with assembly partners, accessing heteroleptic structures of distinct sizes. The third approach investigates CuI cages transforming between [CuI₁₂L₆]¹²⁺ pseudo-hexagonal prismatic and [CuI₈L₄]⁸⁺ tetragonal tubular structures. Using 1,5-naphthylene-bearing tetramine subcomponents to promote secondary interactions, the study reveals that these interactions may collective…
abstract: Metal-organic cages are molecular receptors that enable selective molecular recognition and catalysis, yet most current cage systems employ rigid building blocks that limit guest accommodation and environmental adaptability. Developing cages that combine structural integrity with conformational adaptability remains challenging, requiring balance between pre-organisation for discrete assembly and flexibility for responsive behaviour. This thesis explores dynamic and adaptive metal-organic cage systems through strategic incorporation of flexible subcomponents. Three approaches demonstrate how adaptive self-assembly, dynamic structures, and structural transformations enhance supramolecular host functionality. The first approach introduces a conformationally adaptable ZnII₈L₆ pseudo-cubic cage with tetramine subcomponents featuring 2,6-naphthylene rotary units. These enable independent face switching between endo and exo conformations, dynamically expanding cavity volume to accommodate guests ranging from 46 to 154% of the initial cavity size. The system exemplifies Koshland's induced-fit model, demonstrating synthetic assemblies can mimic biological macromolecule adaptability while maintaining structural integrity. The second approach extends this adaptability to the self-assembly of heteroleptic cages, using the same adaptive tetramine to match triangular building blocks of increasing size. This generates three distinct ZnII₆L₃L'₂ triangular prismatic cages with conformations from near-equilateral to elongated geometries. The 2,6-naphthylene units provide geometric flexibility enabling adaptive matching with assembly partners, accessing heteroleptic structures of distinct sizes. The third approach investigates CuI cages transforming between [CuI₁₂L₆]¹²⁺ pseudo-hexagonal prismatic and [CuI₈L₄]⁸⁺ tetragonal tubular structures. Using 1,5-naphthylene-bearing tetramine subcomponents to promote secondary interactions, the study reveals that these interactions may collective…
author: Xu, Houyang
language: eng
keywords: Self-assembly, Supramolecular chemistry, Metal-organic cages, Coordination chemistry, Host-guest chemistry, Molecular capsules, Coordination cages
license: https://www.repository.cam.ac.uk/bitstreams/b3f105c3-e539-428e-9d3d-97275d9d3e1a/download
license: http://purl.org/NET/rdflicense/allrightsreserved
date published: 2025-08-26
date modified: 2026-07-22T22:24:27Z
provider: Cambridge University
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Cambridge

PropertyValue
property ID: DOI
value: 10.17863/CAM.122614