Construction of slide‐ring polymers based on pillar[5]arene/alkyl chain host−guest interactions

Slide‐ring polymers exhibit distinctive mechanical properties, making them highly promising for applications in emerging fields such as energy storage devices and smart sensing. However, existing slide‐ring polymer systems primarily rely on hydrophilic‐hydrophobic interactions to achieve ring‐axle interlocking in aqueous phases. This reliance limits the construction of slide‐ring networks mainly to water‐soluble polymers, excluding a diverse range of lipophilic polymers. Therefore, it is crucial to introduce efficient construction strategies that facilitate interpenetration in organic solvents, enabling the development of diverse slide‐ring polymers and expanding their range and applications. Herein, by utilizing the pillar[5]arene/alkyl chain host−guest interactions, we successfully facilitated the interpenetration of a pillar[5]arene and poly(caprolactone), enabling the efficient construction of two slide‐ring polymer networks in organic solvents. One of these two slide‐ring polymers demonstrates a unique network deformation mechanism along with outstanding mechanical properties compared with the control covalently cross‐linked polymer network, including maximum stress (4.43 vs 1.98 MPa), maximum strain (1285 vs 330%), and toughness (35.4 vs 3.92 MJ/m3). More importantly, this strategy of making slide‐ring polymers is highly versatile, given the wide range of macrocyclic arenes and alkyl chain‐containing polymers it can accommodate.