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Abstract The integration of mechanically interlocked molecules (MIMs) into polymeric materials has led to the development of mechanically interlocked polymers (MIPs). One class of MIPs that have gained attention in recent years are slide‐ring gels (SRGs), which are generally accessed by crosslinking rings on a main‐chain polyrotaxane. The mobility of the interlocked crosslinking moieties along the polymer backbone imparts enhanced properties onto these networks. An alternative synthetic approach to SRGs is to use a doubly threaded ring as the crosslinking moiety, yielding doubly threaded slide‐ring gel networks (dt‐SRGs). In this study, a photo‐curable ligand‐containing thread was used to assemble a series of metal‐templated pseudo[3]rotaxane crosslinkers that allow access to polymer networks that contain doubly threaded interlocked rings. The physicochemical and mechanical properties of these dt‐SRGs with varying size of the ring crosslinking moieties were investigated and compared to an entangled gel (EG) prepared by polymerizing the metal complex of the photo‐curable ligand‐containing thread, and a corresponding covalent gel (CG). Relative to the EG and CG, the dt‐SRGs exhibit enhanced swelling behavior, viscoelastic properties, and stress relaxation characteristics. In addition, the macroscopic properties of dt‐SRGs could be altered by “locking” ring mobility in the structure through remetalation, highlighting the impact of the mobility of the crosslinks. 

Abstract Vinylogous urethane (VU_O) based polymer networks are widely used as catalyst‐free vitrimers that show rapid covalent bond exchange at elevated temperatures. In solution, vinylogous ureas (VU_N) undergo much faster bond exchange than VU_Oand are highly dynamic at room temperature. However, this difference in reactivity is not observed in their respective dynamic polymer networks, as VU_Oand VU_Nvitrimers prepared herein with very similar macromolecular architectures show comparable stress relaxation and creep behavior. However, by using mixtures of VU_Oand VU_Nlinkages within the same network, the dynamic reactions can be accelerated by an order of magnitude. The results can be rationalized by the effect of intermolecular hydrogen bonding, which is absent in VU_Ovitrimers, but is very pronounced for vinylogous urea moieties. At low concentrations of VU_N, these hydrogen bonds act as catalysts for covalent bond exchange, while at high concentration, they provide a pervasive vinylogous urea ‐ urethane (VU) network of strong non‐covalent interactions, giving rise to phase separation and inhibiting polymer chain dynamics. This offers a straightforward design principle for dynamic polymer materials, showing at the same time the possible additive and synergistic effects of supramolecular and dynamic covalent polymer networks.