Abstract
Designing and building unique cage assemblies attract increasing interest from supramolecular chemists but remain synthetically challenging. Herein, we propose the use of a flexible vertex with adjustable angles to selectively form highly distorted tetrahedral and octahedral cages, for the first time, in which the flexible vertex forms from the synergistic effect of coordination and covalent interactions. The inherent interligand angle of the vertex can be modulated by guest anions present, which allows for the fine-tuning of different cage geometries. Furthermore, the reversible structural transformation between tetrahedral and octahedral cages was achieved by anion exchange monitored by mass spectrometric technique, the smaller anions favoring tetrahedral cages, while the larger anions supporting octahedral cages. Additionally, the KBr-based cage thin films exhibited prominent enhancement of their third-order NLO responses in two or three orders of magnitude compared to those obtained for their corresponding solutions. This work not only provides a new methodology to build irregular polyhedral structures in a controlled and tunable way but also provides access to new kinds of promising functional optical materials.
Highlights
Over the past decades, designing and synthesizing unique supramolecular cages featuring intriguing polyhedral geometries and confined cavities have sparked great interest in supramolecular community [1,2,3,4,5,6]
Coordinated building block binds with Cu(I) ions to form a new flexible vertex that can be used to construct unique supramolecular cages
We have demonstrated that taking advantage of a flexible vertex with adjustable angles represents a feasible and promising strategy for creating new cage assemblies
Summary
Over the past decades, designing and synthesizing unique supramolecular cages featuring intriguing polyhedral geometries and confined cavities have sparked great interest in supramolecular community [1,2,3,4,5,6] In addition to their aesthetically pleasing structures, their unique physical and chemical properties resulting from specific shapes and functionalities endow them wide applications across various fields, ranging from biomedicine [7,8,9], catalysis [10,11,12,13,14], guest encapsulation [15,16,17], separation [18, 19] to luminescent materials [20,21,22]. Being able to adjust the interligand angles at a vertex would represent a highly desirable and major step forward to efficiently expand the existing libraries of molecular cages
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