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Bridging ligand replacement in zeolitic imidazolate frameworks, ZIF-8 and ZIF-67, by 1,2,3-triazole was investigated. A complete substitution of 2-methylimidazole by 1,2,3-triazole resulted in a topological transformation of the parent framework from a sodalite (SOD) network to a diamond (DIA) network.

Herein, a room temperature chemical process to synthesize functional, hollow nanostructures from zeolitic imidazolate framework-8 (ZIF-8) and poly(vinylphosphonic acid) (PVPA) is reported. Syntheses are initiated by physically blending the components-a process that is accompanied first by encapsulation of ZIF-8 crystallites by PVPA and then by fragmentation of the crystallites. The fragmentation process is driven by partial displacement of the methyl-imidazolate ligands of Zn(II) in ZIF-8 by phosphonate groups on PVPA. Differences in rates of diffusion for the components of the reactive mixture yield a Kirkendall-like effect that is expressed as a hollow-particle morphology. The obtained hollow nanostructures feature hybrid shells containing PVPA, ZIF-8, and their cross-reacted products. The hybrid structures display substantial proton conductivities that increase with increasing temperature, even under the anhydrous conditions prevailing at temperatures above the boiling point of water. For example, at T = 413 K the proton conductivity of ZIF-8@PVPA reaches 3.2 (±0.12) × 10(-3) S cm(-1), a value comparatively higher than that for PVPA (or ZIF-8) in isolation. The high value may reflect the availability in the hybrid structures of free (and partially free), amphoteric imidazole species, and their hydrogen-bonding interactions with phosphonate and/or phosphonic acid units. The persistence of ample conductivity at high temperature reflects the elimination of phosphonic acid group dehydration and dimerization-an effect that strikingly degrades the conductivity of pure PVPA under anhydrous conditions.

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The design and fabrication of anhydrous proton exchange membranes are critically important for high temperature proton exchange membrane fuel cell (HT-PEMFC) operating between 100 and 200 °C. Herein, we demonstrate a novel proton conducting membrane consisting of poly(vinyl alcohol) (PVA), poly (2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) and 1,2,4-Triazole, which was fabricated by physical blending, casting and solvent evaporation techniques. The in-situ chemical cross-linking was performed by glutaraldehyde (GA) to improve the water management of the membranes. The molecular structure of the membranes and intermolecular interactions between the constituents were confirmed by Fourier-transform infrared spectroscopy (FT-IR). The surface and cross-section morphologies of the membranes were observed by scanning electron microscopy (SEM). The thermal stability performance of the membranes was studied with thermogravimetric analysis (TGA). In order to determine the physico-chemical properties of the membranes, water uptake (WU), dimensional change and ion exchange capacity (IEC) tests were carried out. The proton conductivities of composite membranes increase with the temperature and the temperature dependencies exhibit an

A new solution-processable and air-stable liquid-crystalline n-channel organic semiconductor (2,2'-(2,8-bis(5-(2-octyldodecyl)thiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile, α,ω-2OD-TIFDMT) with donor-acceptor-donor (D-A-D) π conjugation has been designed, synthesized, and fully characterized. The new semiconductor exhibits a low LUMO energy (-4.19 eV) and a narrow optical bandgap (1.35 eV). The typical pseudo-focal-conic fan-shaped texture of a hexagonal columnar liquid-crystalline (LC) phase was observed over a wide temperature range. The spin-coated semiconductor thin films show the formation of large (≈0.5-1 μm) and highly crystalline platelike grains with edge-on molecular orientations. Low-temperature-annealed (50 °C) top-contact/bottom-gate OFETs have provided good electron mobility values as high as 0.11 cm (V s) and high I /I ratios of 10 to 10 with excellent ambient stability. This indicates an enhancement of two orders of magnitude (100×) when compared with the β-substituted parent semiconductor, β-DD-TIFDMT (2,2'-(2,8-bis(3-dodecylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile). The current rational alkyl-chain engineering route offers great advantages for D-A-D π-core coplanarity in addition to maintaining good solubility in organic solvents, and leads to favorable optoelectronic/physicochemical characteristics. These remarkable findings demonstrate that α,ω-2OD-TIFDMT is a promising semiconductor material for the development of n-channel OFETs on flexible plastic substrates and LC-state annealing of the columnar liquid crystals can lower the electron mobility for transistor-type charge transport.

Herein, we use linker fragmentation approach to introduce boronic acid moieties as functional defects into Zr-based metal-organic frameworks (MOFs, UiO-66). Our findings show that the amount of permanently incorporated boronic acid containing ligand is directly dependent on the synthesis method. The accessible boronic acid moieties in the pore surfaces significantly improve the hydrogen uptake values, which are 3.10 and 3.44 wt % at 21 bar, 77 K for dimethylformamide (DMF)/HO and DMF/HCI synthesis methods, respectively. Also, CO selectivity of the resulting MOFs over N and CH significantly increases due to the quadrupolar interaction between active surfaces and CO molecules. To the best of our knowledge, both hydrogen storage and selectivity of CO for UiO-66 are the highest reported values in the literature to date. Furthermore, another striking result that emerged from the high-pressure hydrogen uptake isotherms is the direct correlation between the defects and hysteric adsorption behavior, which may result in the shift from rigidity to flexibility of the framework due to the uncoordinated sites.

Amorphous metal‐organic frameworks (MOFs) and the amorphization of crystalline MOFs under mechanical stimuli are attracting considerable interest in last few years. However, we still have limited knowledge on their atomic arrangement and the physical origin of crystalline‐to‐amorphous phase transitions under mechanical stimuli. In this study, ab initio simulations within a generalized gradient approximation are carried out to investigate the high‐pressure behavior of MOF‐5. Similar to the previous experimental findings, a pressure‐induced amorphization is observed at 2 GPa through the simulations. The phase transformation is an irreversible first order transition and accompanied by around 68% volume collapse. Remarkably, the transition arises from local distortions and, contrary to previous suggestions, does not involve any bond breaking and formation. Additionally, a drastic band gap closure is perceived for the amorphous state. This study has gone some way towards enhancing our understanding of pressure‐induced amorphization in MOFs.