Dynamic Covalent Self-sorting in Molecular and Polymeric Architectures Enabled by Spiroborate Bond Exchange

Area of Science:

• Dynamic Covalent Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• Self-sorting is crucial for creating specific molecular architectures in complex systems.
• Most self-sorting studies focus on non-covalent interactions, with covalent systems being less explored.
• Dynamic covalent chemistry offers pathways to construct complex molecular structures through reversible bond formation.

Purpose of the Study:

• To demonstrate the dynamic nature of spiroborate linkages for self-sorting.
• To investigate the transformation between polymeric and molecular architectures driven by spiroborate bond exchange.
• To achieve the formation of a shape-persistent molecular cage from a 1D polymer via self-sorting.

Main Methods:

• Utilizing spiroborate linkages, which exhibit dynamic covalent character.
• Inducing self-sorting through bond exchange between a macrocycle and a 1D helical polymer.
• Characterizing the resulting molecular cage structure using single-crystal X-ray diffraction.

Main Results:

• The spiroborate linkage was shown to be dynamic, enabling bond exchange.
• Self-sorting occurred between a macrocycle and a 1D helical polymer.
• A thermodynamically favored molecular cage was formed and structurally confirmed.

Conclusions:

• This work is the first to show a 1D polymer transforming into a shape-persistent molecular cage via dynamic covalent self-sorting.
• Spiroborate-based dynamic covalent chemistry provides a novel route for constructing complex molecular architectures.
• The findings pave the way for designing new responsive spiroborate materials and systems.