The first wide-view image of multiple structural and phase transformations for MOFs, ranging from crystal state transformations to the extreme limit approaching liquid/glass phase, was presented. The process involves i) an initial crystalline transformation from square-layer framework [Co2(pybz)2(CH3COO)2] ⋅ DMF (Co2) to a 3-fold interpenetrated and ordered vacancies contained framework [Co(pybz)2(CH3OH)2] ⋅ 2CH3OH (CoM) due to in situ disassemble-reassemble, ii) thermal induced departure of a pair of cis-form coordinated methanol in CoM leads to amorphous framework a-dCoM, iii) glass transition to super-cooled liquid scl-dCoM, iv) obtaining MOF glass g-dCoM upon quenching the super-cooled liquid, and v) re-crystallization of super-cooled liquid generates 6-fold interpenetrated dia-net framework [Co(pybz)2]6n (rec-dCoM) under further heating. The access to glass from CoM, provides a new self-perturbation strategy to create MOF glasses without melting. The wider pore size distribution in amorphous/glassy MOFs than crystalline precursor achieved the first time selective hydrocarbon gas separation by breakthrough experiments, which bring efficient separation of 1 : 99 C2H2/C2H4 by either a-dCoM or g-dCoM and produce polymer grade C2H4 with purity≥99.5 % after a single adsorption process. Furthermore, the mixture of 50 : 50 C3H6/C3H8 can be separated by a-dCoM.

Glassy and liquid state metal-organic frameworks (MOFs) are emerging type of materials subjected to intense research for their rich physical and chemical properties. In this report, we obtained the first glassy MOF that involves metal-carboxylate cluster building units via multi-stage structural transformations. This MOF is composed of linear [Mn-3(COO)(6)] node and flexible pyridyl-ethenylbenzoic linker. The crystalline MOF was first perturbed by vapor hydration and thermal dehydration to give an amorphous state, which can go through a glass transition at 505 K into a super-cooled liquid. The super-cooled liquid state is stable through a wide temperature range of 40 K and has the largest fragility index of 105, giving a broad processing window. Remarkably, the super-cooled liquid can not only be quenched into glass, but also recrystallize into the initial MOF when heated to a higher temperature above 558 K. The mechanism of the multi-stage structural transformations was studied by systematic characterizations of in situ X-ray diffraction, calorimetry, rheological, spectroscopic and pair-distribution function analysis. These multi-stage transformations not only represent a rare example of high temperature coordinative recognition and self-assembly, but also provide new MOF processing strategy through crystal-amorphous-liquid-crystal transformations.

Many living tissues, such as muscle, become mechanically stronger with growth. Yet, synthetic hydrogels usually exhibit an opposite size‐mechanical property relation, that is, swelling‐weakening behavior. Herein, a series of swollen yet strengthened polyampholyte (PA) hydrogels are developed via a simple metal‐ion solution soaking strategy. In this strategy, a dynamic PA hydrogel (with ionic bonds) is dialyzed in ZrOCl 2 solutions (Step‐I) and deionized water (Step‐II) successively to obtain equilibrated hydrogels. Due to the specific Zr 4+ ions and PA network structure, Step‐I takes several months with sample size and mechanical performance increasing continuously, while Step‐II only needs several days. Through this strategy, the resultant hydrogel networks are reorganized and eventually constructed by ionic and metalligand bonds, enabling the swelling yet strengthening behavior. A systematic study confirms that dialysis time in Step‐I and corresponding ZrOCl 2 concentration can significantly affect the multiphase microstructures of the hydrogels, resulting in different mechanical enhancements. The optimized hydrogel possesses 39.2 MPa of Young's modulus and 3.7 MPa of tensile strength, which are 302 and 5.5 times these of the original PA gel, respectively. Despite distinct swelling, these hydrogels still mechanically surpass many existing high‐performance hydrogels. This study opens a novel pathway for fabricating swollen yet strengthened hydrogels.

Despite existing in biological systems, developing synthetic polyampholyte (PA) hydrogels constructed by both ionic and metal–ligand bonds remains challenging. Herein, a simple secondary equilibrium approach is proposed to fabricate strong and tough PA hydrogels via the synergy of ionic and metal–ligand bonds. The original PA gels (constructed by ionic bonds) are first dialyzed in multivalent metal‐ion solutions to reach a swelling equilibrium and then moved to deionized water to dialyze excess free ions to achieve a new equilibrium. Through this approach, the original PA gel network can be optimized and eventually constructed by ionic and metal–ligand bonds, enabling a synergistic reinforcement. By selecting different original PA gel systems and diverse multivalent metal‐ions, the proposed approach is proved to be generalizable to fabricate strong and tough PA gels. Additionally, the hydrogels have stable ion‐conductivity even at the water‐equilibrium state, making them promising as strain sensors. The viscoelastic and elastic contributions to the mechanical properties of the hydrogels by a viscoelastic model are also discussed to further understand the strengthening and toughening mechanisms. The proposed strategy is simple but effective for achieving strong and tough PA‐based hydrogels. This study also provides new insights for PA hydrogels in electrolyte environments.

Intelligent hydrogels that simultaneously exhibit excellent toughness, self-healing ability and photoelectronic responsiveness are in high demand but are greatly challenging to prepare. Inspired by the hierarchical structure of fluorescent proteins in jellyfish and biomembranes in nature, herein, a facile and universal all-in-one strategy is demonstrated to construct fluorescent, electrically responsive and ultratough self-healing hydrogels via aqueous self-assembly of polyelectrolyte-surfactant micelles with hierarchical structures and functionality. The self-assembled 2-ureido-4-[1H]-pyrimidone (UPy) hydrophobic core containing reversible physical crosslinks embedded in micelles leads to a durable network structure with excellent toughness and self-healing ability. Moreover, dramatically enhanced fluorescence emission is obtained due to the formation of nanoclusters with electron-rich moieties that show restricted intramolecular motion induced by hydrogen bonding networks from UPy dimer aggregation. The micelle-incorporated sulfonic acid groups mimic the function of biological membrane proteins that deftly control the micelle size, leading to electro-responsiveness, enhanced toughness and fluorescence emission.

A kind of dual physically crosslinked hydrogel with pH-triggered self-healing and shape memory properties is reported.