Dynamics of ring-containing polymers: Macromolecular rotaxanes, polyrotaxanes and slide-ring networks

Abstract

A mechanical bond serves as a distinctive approach for harnessing the most beneficial features of both covalent and supramolecular chemistries, offering stability and structural adaptability owing to its unique dynamic nature. Molecules formed by mechanical bonding, known as mechanically interlocked molecules (MIMs) including catenanes, rotaxanes, and knots have opened new possibilities. Notably, the introduction of mechanically interlocked structures into polymers has led to the emergence of novel polymeric materials referred to as mechanically interlocked polymers (MIPs), such as polyrotaxanes and polycatenanes. The interlocked nature of these architectures can lead to particular conformational freedom and high mobility of their components, resulting in exceptional properties, such as ultra-stretchability, toughness, and immediate recoverability. These properties have found potential applications in diverse fields, including the development of tough hydrogels, scratch-resistant coatings, smart actuators, and batteries. Recent years have witnessed a surge in the synthesis and investigation of a diverse array of rotaxane-based MIPs, an essential class that has enabled researchers to begin grasping the impact of incorporating mechanical bonds within polymer structures, and of their mobility, on material properties. In this review, an overview of the dynamics of ring-containing polymers is presented. The review encompasses macromolecular rotaxanes, polyrotaxanes, and slide-ring networks, including the role of ring mobility in shaping the dynamics and properties of rotaxane polymers.