A family of metal-organic frameworks (MOFs) and coordination polymers (CPs) based on dynamic structural elements are of great fundamental and commercial interest addressing modern problems in controlled molecular separation, catalysis and even data processing. Herein, the endurance and fast structural dynamics of such materials at ambient conditions are still a fundamental challenge. Here, we report on the design of a series of Cu-based CPs [Cu(bImB)Cl2](1) and [Cu(bImB)2Cl2] (2), where bImB is 1,4-bis(imidazol-1-yl)butane), with flexible ligand packed into one-and two-dimensional (1D, 2D) structures demonstrating dimensionality mediated

Polymers with embedded metal–organic frameworks (MOFs) have been of interest in research for advanced applications in gas separation, catalysis and sensing due to their high porosity and chemical selectivity. In this study, we utilize specific MOFs with high thermal stability and non-centrosymmetric crystal structures (zeolitic imidazolate framework, ZIF-8) in order to give an example of MOF–polymer composite applications in nonlinear optics. The synthesized MOF-based polymethyl methacrylate (PMMA) composite (ZIF-8–PMMA) demonstrates the possibility of the visualization of near-infrared laser beams in the research lab. The resulting ZIF-8–PMMA composite is exposed to a laser under extreme conditions and exhibits enhanced operating limits, much higher than that of the widely used inorganic materials in optics. Overall, our findings support the utilization of MOFs for synthesis of functional composites for optical application.

Metal-organic frameworks (MOFs) represent a unique platform for fabrication of nanoparticles (NPs) of diverse composition and crystallinity. The growth of NPs from constituent parts of MOFs is usually initiated by external stimuli such as temperature, light and electron irradiation. Herein, the kinetics and NP growth mechanisms remain unexplored. Here, we utilized electron irradiation to initiate the nucleation and growth of crystalline Cu NPs of tunable size from several nanometers to hundreds of nanometers inside MOF as a precursor. Simultaneously, the process of the NPs growth, captured in real time using transmission electron microscope, demonstrates the evolution of their size, shape and spatial distribution. We also analyze the NP growth by the classical kinetic theory taking into account a phase transformation. Our results contribute to crystal engineering and developing of functional MOF-based nanocomposites.

Metal–organic frameworks (MOFs) have been recently explored as crystalline solids for conversion into amorphous phases demonstrating non-specific mechanical, catalytic, and optical properties. The real-time control of such structural transformations and their outcomes still remain a challenge. Here, we use in situ high-resolution transmission electron microscopy with 0.01 s time resolution to explore non-thermal (electron induced) amorphization of a MOF single crystal, followed by transformation into an amorphous nanomaterial. By comparing a series of M-BTC (M: Fe3+, Co3+, Co2+, Ni2+, and Cu2+; BTC: 1,3,5-benzentricarboxylic acid), we demonstrate that the topology of a metal cluster of the parent MOFs determines the rate of formation and the chemistry of the resulting phases containing an intact ligand and metal or metal oxide nanoparticles. Confocal Raman and photoluminescence spectroscopies further confirm the integrity of the BTC ligand and coordination bond breaking, while high-resolution imaging with chemical and structural analysis over time allows for tracking the dynamics of solid-to-solid transformations. The revealed relationship between the initial and resulting structures and the stability of the obtained phase and its photoluminescence over time contribute to the design of new amorphous MOF-based optical nanomaterials.

Metal‐organic frameworks (MOFs), demonstrating structural response on external stimuli, represent a promising family of crystalline materials for microelectronic and data storage devices. Herein, manipulation with MOF structure at the nanometer scale for the device miniaturization is still a challenge. Here, mechanical recording and reading the nanometer scale patterns onto flexible 2D MOF at ambient conditions are reported. Treatment of the MOF surface with a hot solvent decreases the roughness up to 1/7 of the layer thickness. Therefore, an atomic force microscope probe is allowed to cause the deformations with the spatial resolution up to 25 nm (≈0.1 Tbyte inch−2 storage density) and the depth from 0.4 nm. Selective chemical etching by the solvent can further develop the pattern, while the integrity of the MOF structure maintains. The realization of the "read‐only‐memory" concept on flexible MOF at ambient conditions paves the way for next‐generation sustainable data storage materials.