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Abstract A liquid crystalline elastomer (LCE) network consisting of dynamic covalent bonds (DCBs) is referred as a LCE vitrimer. The mesogen alignment and the network topology can be reprogrammed locally in the LCE vitrimer by activating the bond exchange reactions using an external stimulus. After removal of the external stress, a new network is formed and the reprogrammed shape can be fixed, leading to a different set of the physical properties of the LCE vitrimers. Herein, this type of emerging materials is reviewed by a brief introduction of the fundamentals of LCEs, followed by discussions of various DCBs and the design principles for LCE vitrimers. After a presentation of different strategies to improve the stability and reprogrammability of the registered mesogen alignment, approaches to prepare LCE vitrimers with complex shapes and their actuations are discussed. Potential applications such as self‐healing and recycling, mechanochromic effects, and post‐functionalization of nanopores are also reviewed, followed by the conclusion of the remaining challenges and opportunities. 

Abstract Maxwell lattices possess distinct topological states that feature mechanically polarized edge behaviors and asymmetric dynamic responses protected by the topology of their phonon bands. Until now, demonstrations of non‐trivial topological behaviors from Maxwell lattices have been limited to fixed configurations or have achieved reconfigurability using mechanical linkages. Here, a monolithic transformable topological mechanical metamaterial is introduced in the form of a generalized kagome lattice made from a shape memory polymer (SMP). It is capable of reversibly exploring topologically distinct phases of the non‐trivial phase space via a kinematic strategy that converts sparse mechanical inputs at free edge pairs into a biaxial, global transformation that switches its topological state. All configurations are stable in the absence of confinement or a continuous mechanical input. Its topologically‐protected, polarized mechanical edge stiffness is robust against broken hinges or conformational defects. More importantly, it shows that the phase transition of SMPs that modulate chain mobility, can effectively shield a dynamic metamaterial's topological response from its own kinematic stress history, referred to as “stress caching”. This work provides a blueprint for monolithic transformable mechanical metamaterials with topological mechanical behavior that is robust against defects and disorder while circumventing their vulnerability to stored elastic energy, which will find applications in switchable acoustic diodes and tunable vibration dampers or isolators.