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Stimuli-responsive smart materials that can undergo reversible chemical/physical changes under external stimuli such as mechanical stress, heat, light, gas, electricity, and pH, are currently attracting increasing attention in the fields of sensors, actuators, optoelectronic devices, information storage, medical applications, and so forth. The current smart materials mostly concentrate on polymers, carbon materials, crystalline liquids, and hydrogels, which have no or low structural order (i.e., the responsive groups/moieties are disorderly in the structures), inevitably introducing deficiencies such as a relatively low response speeds, energy transformation inefficiencies, and unclear structure-property relationships. Consequently, crystalline materials with well-defined and regular molecular arrays can offer a new opportunity to create novel smart materials with improved stimuli-responsive performance. Crystalline materials include framework materials (e.g., metal-organic frameworks, MOFs; covalent organic frameworks, COFs) and molecular crystals (e.g., organic molecules and molecular cages), which have obvious advantages as smart materials compared to amorphous materials. For example, responsive groups/moieties can be uniformly installed in the skeleton of the crystal materials to form ordered molecular arrays, making energy transfer between external-stimulus signals and responsive sites much faster and more efficiently. Besides that, the well-defined structures facilitate in situ characterization of their structural transformation at the molecular level by means of various techniques and high-tech equipment such as in situ spectra and single-crystal/powder X-ray diffraction, thus benefiting the investigation and understanding of the mechanism behind the stimuli-responsive behaviors and structure-property relationships. Nevertheless, some unsolved challenges remain for crystalline smart materials (CSMs), hampering the fabrication of smart material systems for practical applications. For instance, as the materials' crystallinity increases, their processability and mechanical properties usually decrease, unavoidably hindering their practical application. Moreover, crystalline smart materials mostly exist as micro/nanosized powders, which are difficult to make stimuli-responsive on the macroscale. Thus, developing strategies that can balance the materials' crystallinity and processability and establishing macroscale smart material systems are of great significance for practical applications.In this Account, we mainly summarize the recent research progress achieved by our groups, including (i) the rational design and fabrication of new stimuli-responsive crystalline smart materials, including molecular crystals and framework materials, and an in-depth investigation of their response mechanism and structure-property relationship and (ii) creating chemical/physical modification strategies to improve the processability and mechanical properties for crystalline materials and establishing macroscale smart systems for practical applications. Overall, this Account summarizes the state-of-the-art progress of stimuli-responsive crystalline smart materials and points out the existing challenges and future development directions in the field.

Fabricating mechanically responsive actuators that can efficiently convert external stimuli into mechanical work is of great significance for real‐world applications. Herein, we rationally design a class of rigid–flexible coupling crystalline crosslinked polymers (CCPs) to fabricate vapomechanically responsive actuators. Interfacial condensation reactions of flexible macromers with rigid monomers afford a series of freestanding CCP membranes. Notably, it is the first example where crosslinked polymers show high crystallinity and porosity. Moreover, the CCP membranes exhibit good mechanical properties and interesting vapor‐triggered actuation performance, which is reversible and repeatable. We find that the unusual polymer structures, high vapor sorption, and anisotropic membranes contribute to the directional deformation performance of the CCP actuators. The synthesis approach in this work provides new insights into the design and fabrication of smart materials for advanced applications. [ABSTRACT FROM AUTHOR]

Traditional ozone sensing and removal materials still suffer from high energy consumption and low efficiency. Thus, seeking new ozone‐responsive materials with high efficiency and broad working conditions is of great significance. Herein, we first developed covalent organic frameworks (COFs) for smart sensing and efficient removal of ozone. Notably, imine‐based COFs possess dramatically fast optical responses (<1 s) to ozone as low as 0.1 ppm under broad working conditions (e.g., in the presence or absence of moisture, room temperature). Moreover, we found that imine‐based COFs can also be applied as excellent ozone removers that can efficiently reduce the ozone concentration below the recommended safety limit (<0.1 ppm) for humans. The mechanism for the performance of imine‐based COFs was unveiled in‐depth by various characterization techniques and analyses. This study not only provides a new type of advanced materials for ozone sensing and removal but also broadens the application scope of COFs. [ABSTRACT FROM AUTHOR]