A Novel Mechano-Synthesized Zeolitic Tetrazolate Framework for a High-Performance Triboelectric Nanogenerator and Self-Powered Selective Neurochemical Detection.

Designing a high-performing triboelectric novel material with eco-friendly, rapid, and cost-effective synthesis is the future of material research in triboelectric nanogenerators (TENG). We report a mechanochemical ball mill synthesis of a zeolitic tetrazolate framework (ZTF-8) that is isostructural with the well-known zeolitic imidazolate framework ZIF-8. ZTF-8 is extremely stable in water, 0.1 M aqueous acid/base solutions for 75 days at 25 °C, and boiling water (100 °C) for 7 days. Kelvin probe force microscopy and molecular electrostatic surface potential computational analysis exhibited that ZTF-8 has a very high positive surface potential. Atomic force microscopy and three-dimensional digital microscopy studies reveal the high roughness profile in the ZTF-8 film. The unique structure, exceptional acid/base stability, good dielectric property, and high roughness profile combined with the extremely electropositive nature of ZTF-8 make it a suitable candidate as a polymer-free triboelectric positive material in TENG with outstanding performance (power density of 720 mW/m2). High triboelectric output was further validated using the COMSOL Multiphysics simulation tool. Simple mechanical hand tapping of the ZTF-based TENG (ZTF-TENG) device generates high electric output, which was practically used to power numerous low-powered devices like tally counter, clinical thermometer, and digital clock and also illuminates 125 light-emitting diodes. In addition, the efficiency of ZTF-TENG was utilized as a self-powered device for a selective dopamine (DA) sensor with good sensitivity (377.76 mV/µM/cm2), wide range linearity (5-120 µM), and excellent limit of detection (0.42 µM).

Hydroxide Ion Conduction through Viologen-Based Covalent Organic Frameworks (vCOFs): An Approach toward the Advancement.

Alkaline fuel cells rely on the movement of hydroxide anions (OH-) for their operation, yet these anions face challenges in efficient conduction due to their limited diffusion coefficient and substantial mass compared to proton (H+) transport. Within the covalent organic framework structure, ordered channels offer a promising solution for the OH- ion transport. Herein, we synthesized a cationic covalent organic framework (vTAPA) via the solvothermal-assisted Zincke reaction. vTAPA showcases excellent stability in harsh basic solution (12 M) and a wide range of pH. This framework facilitates OH- conduction through its one-dimensional network through the anion exchange process. We employed various tertiary ammonium salts (tetramethyl, tetraethyl, and tetrabutyl ammonium hydroxide) to exchange trapped anionic chloride ions inside the vTAPA structure with OH- ions. The density functional theory (DFT) study exhibited that the anion exchange process is very favorable, as the vTAPA framework offers preferable interaction sites for OH- ions. The impact of steric hindrance from these tertiary ammonium salts on the OH- conduction performance was extensively investigated. Butyl@vTAPA exhibited a high OH- ion conductivity of 1.05 × 10-4 S cm-1 at 90 °C under 98% relative humidity (RH). Our uniquely designed cationic covalent organic frameworks (COF) created a platform for a preferential transport network of hydroxide ions, and this is the first report of directly used COFs for hydroxide ion conduction without any vigorous postsynthetic modification.

A series of isostructural metal-organic frameworks for an enhanced electro-catalytic oxygen evolution reaction.

Three new isostructural MOFs (ZnTIA, CoTIA and CdTIA) were synthesized by the solvothermal synthesis of the organic linker 5-triazole isophthalic acid (5-TIA) with the transition metals Zn(II), Co(II) and Cd(II) in the presence of the structure directing agent tetramethyl ammonium chloride (TMA). These three MOFs were characterized thoroughly by ScXRD, PXRD, FT-IR, TGA, BET and SEM. They have excellent thermal and water stabilities. Among all these MOFs mentioned, pristine CoTIA exhibited excellent electrocatalytic activity toward the oxygen evolution reaction (OER). It exhibits a Tafel slope of 68.9 mV dec-1 with an overpotential of 337 mV at 10 mA cm-2 current density. The OER activity of the CoTIA MOF is relatively equivalent to that of the state-of-the-art catalyst (RuO2). Furthermore, the mechanical stability of crystalline ZnTIA, CoTIA and CdTIA MOFs was tested under ball mill pressure. The result showed that all the MOFs exhibit low tolerance to mechanical force because their structure was highly distorted or collapsed under such pressure, which is reflected by their poor electrocatalytic OER activity.

Reticular synthesis of two-dimensional ionic covalent organic networks as metal-free bifunctional electrocatalysts for oxygen reduction and evolution reactions.

Bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are the heart of metal-air batteries, fuel cells, and other energy storage systems. Here, we report a series of a novel class of redox-active viologen-based ionic covalent organic networks (vCONs) which are directly used as metal-free bifunctional electrocatalysts towards ORR and OER applications. These vCONs (named vGC, vGAC, vMEL and vBPDP) were synthesized by the well-known Zincke reaction. The installation of redox-active viologen moieties among the extended covalent organic architectures played a crucial role for exceptional acid/base stability, as well as bifunctional ORR and OER activities, confirmed by the cyclic voltammetry (CV) curves. Among all of them, vBPDP showed high ORR efficiency with a half-wave potential of 0.72 V against a reversible hydrogen electrode (RHE) in 1 M KOH electrolyte. In contrast, vMEL demonstrated high OER activity with an overpotential of 320 mV at a current density of 10 mAcm-2 and a Tafel slope of 109.4 mV dec-1 in 1 M KOH electrolyte solution. This work is exceptional and unique in terms of directly used pristine ionic covalent organic networks that are used as bifunctional (ORR and OER) electrocatalysts without adding any metals or conductive materials.

Robust Zeolitic Tetrazole Framework for Electrocatalytic Dopamine Detection with High Selectivity.

A novel zeolitic tetrazolate framework (ZTF-8) has been synthesized by solvent-free heat-assisted (70 °C) mechanochemical grinding of zinc acetate and 5-methyl tetrazole in the presence of NaOH powder. The structure of ZTF-8 adopts the zeolitic sodalite (SOD) topology with uncoordinated N-heteroatom sites and resembles the structure of the well-known zeolitic imidazole framework ZIF-8. ZTF-8 is exceptionally stable in 0.1 M aqueous acid and base solutions for 60 days at 25 °C. The unique structure with uncoordinated N-heteroatom active sites and exceptional stability of ZTF-8 facilitated the electrocatalytic oxidation of dopamine to dopamine quinone at neutral pH. Without any postsynthetic modification, ZTF-8 is directly used for the facile electrochemical detection of dopamine over a wide range of concentrations (5-550 µM) with a high sensitivity (2410.8 µA mM-1 cm-2). It also demonstrated promising selectivity over other interferents of similar oxidation potential, such as ascorbic acid and uric acid. The DFT study revealed that the ZTF-8 framework has a higher binding energy (-145.07 kJ/mol) and stronger interaction with dopamine than its isostructural ZIF-8 structure (-130.42 kJ/mol).

Mechanical Alloying in Zeolitic Imidazolate Framework for Enhanced Photocatalytic Dye Degradation.

A ball milling approach has been performed for isostructural ZnZIF-8 and CoZIF-8 in a 1:1 molar ratio to produce the amorphous (a) solid solution state (aZn0.5Co0.5ZIF-8). It further transformed to a crystalline (c) solid solution state (cZn0.5Co0.5ZIF-8) by exposing 95% relative humidity (RH) at 25 °C for 72 h. Unique heterometal solid solution structure and high catalytic active sites of aZn0.5Co0.5ZIF-8 showed excellent photocatalytic performance for the degradation of methylene blue dye under visible light source. The catalytic efficiency of aZn0.5Co0.5ZIF-8 (97.9%) is much higher than the pristine (p) as well as the amorphous state (a) of ZnZIF-8/CoZIF-8 and cZn0.5Co0.5ZIF-8.

Phase Purity Regulated by Mechano-Chemical Synthesis of Metal-Organic Frameworks for the Electrocatalytic Oxygen Evolution Reaction.

Three new metal organic frameworks (ZnTIA-1mc, CuTIA-1mc, and CoTIA-1mc) were synthesized by the mechanochemical grinding (mc) method in the unadulterated form. They compared with their solvothermally synthesized (st) counterparts, where the mixtures of isomeric forms have been isolated. Kinetics study with the function of grinding time during the mechanosynthesis process revealed the formation of new metastable phases. Less crystallinity and short of mechanical defects in the structure of synthesized mc metal organic frameworks showed enhanced electrocatalytic activity toward oxygen evolution reaction (OER). Among all, CoTIA-1mc showed high OER activity with 289 mV overpotential, 10 mA cm-2 current density, and 55.4 mV dec-1 Tafel slope in 1 M KOH which is close to the commercially used RuO2.

NLO-active Y-shaped ferrocene conjugated imidazole chromophores as precursors for SHG polymeric films.

New Y-shaped ferrocene conjugated imidazole chromophores were prepared and fully characterized. The Y-shaped structure was confirmed by the single crystal X-ray diffraction technique. The chromophores show interesting second-order nonlinear optical (NLO) properties in solution, as determined by the Electric-Field Induced Second Harmonic generation (EFISH) technique. Remarkably, the trifluoro substituted compound 3 is characterized by a high µßEFISH value and has good potential as a molecular building block for composite films with Second Harmonic Generation (SHG) properties. For all compounds, the dipole moments and frontier orbital energies were calculated by the Density Functional Theoretical method.

Inkless Writing and Self-Erasing Security Feature of (Z)-1,2-Diarylacrylonitrile-Based Materials: A Confidential Data Communication.

Development of a novel organic luminescent material for inkless writing, and self-erasing application is a remarkable solution to reduce paper waste, recycling cost in the printing industry. These innovative materials also offer to reduce global warming due to the lower consumption of paper made from plants. To this endeavor, herein we report the design, synthesis and simple material fabrication of a donor-acceptor type (Z)-1,2-diarylacrylonitrile (1) compound, which in solid state displayed highly contrast and reversible vapochromism under the visible light as well as UV light. We found a unique multiphase luminescence switching from green (λmax = 535 nm) to yellow (λmax = 566 nm) and to orange-red (λ = 580, 640 nm) in solid state. This multiphase switching is induced through the gradual exclusion of entrapped DMSO molecules from the crystalline rod-like materials. Utilizing this purely organic material, we have demonstrated reversible inkless writing/printing on a cellulose strip by employing photothermal effect of sunlight in which sunlight acts as an "inkless pen". We were able to print complex designs utilizing this technique, which is invisible in ambient light and brighter in UV light. To our delight, the writing is self-erasable on keeping at sunlight for the prolonged period, upon keeping at ambient temperature, or instantly on warming. This remarkably smart function of our material offers cost-effective and environmentally benign technique for security data communication and confidential data printing.

Distinct Mechanoresponsive Luminescence, Thermochromism, Vapochromism, and Chlorine Gas Sensing by a Solid-State Organic Emitter.

In this study, we report a synthetically simple donor-acceptor (D-A)-type organic solid-state emitter 1 that displays unique fluorescence switching under mechanical stimuli. Orange and yellow emissive crystals of 1 (1O, 1Y) exhibit an unusual "back and forth" fluorescence response to mechanical force. Gentle crushing (mild pressure) of the orange or yellow emissive crystal results in hypsochromic shift to cyan emissive fragments (λem = 498-501 nm) with a large wavelength shift Δλem = -71 to -96 nm, while further grinding results in bathochromic swing to green emissive powder λem = 540-550 nm, Δλem = +40 to 58 nm. Single-crystal X-ray diffraction study reveals that molecules are packed by weak interactions, such as C-H···π, C-H···N, and C-H···F, which facilitate intermolecular charge transfer in the crystal. With the aid of structural, spectroscopic, and morphological studies, we established the interplay between intermolecular and intramolecular charge-transfer interaction that is responsible for this elusive mechanochromic luminescence. Moreover, we have also demonstrated the application of this organic material for chlorine gas sensing in solid state.

Mechanical Alloying of Metal-Organic Frameworks.

The solvent-free mechanical milling process for two distinct metal-organic framework (MOF) crystals induced the formation of a solid solution, which is not feasible by conventional solution-based syntheses. X-ray and STEM-EDX studies revealed that performing mechanical milling under an Ar atmosphere promotes the high diffusivity of each metal ion in an amorphous solid matrix; the amorphous state turns into the porous crystalline structure by vapor exposure treatment to form a new phase of a MOF solid solution.

Reactivity and operational stability of N-Tailed TAMLs through kinetic studies of the catalyzed oxidation of orange†II by H2 O2 : synthesis and X-ray structure of an N-phenyl TAML.

Invited for the cover of this issue are Terrence J. Collins and co-workers at Carnegie Mellon University (USA) and the National Chemical Laboratory (India). The image depicts five generations of tetraamido macrocyclic ligand (TAML) activators, which are small molecule, full-functional mimics of oxidizing enzymes that arguably outperform the peroxidase enzymes they mimic. Read the full text of the article at 10.1002/chem.201406061.

Reactivity and operational stability of N-tailed TAMLs through kinetic studies of the catalyzed oxidation of orange†II by H2 O2 : synthesis and X-ray structure of an N-phenyl TAML.

The catalytic activity of the N-tailed ("biuret") TAML (tetraamido macrocyclic ligand) activators [Fe{4-XC6 H3 -1,2-(NCOCMe2 NCO)2 NR}Cl](2-) (3; N atoms in boldface are coordinated to the central iron atom; the same nomenclature is used in for compounds 1 and 2 below), [X, R=H, Me (a); NO2 , Me (b); H, Ph (c)] in the oxidative bleaching of Orange II dye by H2 O2 in aqueous solution is mechanistically compared with the previously investigated activator [Fe{4-XC6 H3 -1,2-(NCOCMe2 NCO)2 CMe2 }OH2 ](-) (1) and the more aggressive analogue [Fe(Me2 C{CON(1,2-C6 H3 -4-X)NCO}2 )OH2 ](-) (2). Catalysis by 3 of the reaction between H2 O2 and Orange II (S) occurs according to the rate law found generally for TAML activators (v=kI kII [Fe(III) ][S][H2 O2 ]/(kI [H2 O2 ]+kII [S]) and the rate constants kI and kII at pH 7 both decrease within the series 3 b>3 a>3 c. The pH dependency of kI and kII was investigated for 3 a. As with all TAML activators studied to-date, bell-shaped profiles were found for both rate constants. For kI , the maximal activity was found at pH 10.7 marking it as having similar reactivity to 1 a. For kII , the broad bell pH profile exhibits a maximum at pH about 10.5. The condition kI ≪kII holds across the entire pH range studied. Activator 3 b exhibits pronounced activity in neutral to slightly basic aqueous solutions making it worthy of consideration on a technical performance basis for water treatment. The rate constants ki for suicidal inactivation of the active forms of complexes 3 a-c were calculated using the general formula ln([S0 ]/[S∞ ])=(kII /ki )[Fe(III) ]; here [Fe(III) ], [S0 ], and [S∞ ] are the total catalyst concentration and substrate concentration at time zero and infinity, respectively. The synthesis and X-ray characterization of 3 c are also described.

Structural isomerism leading to variable proton conductivity in indium(III) isophthalic acid based frameworks.

Proton conductivity has been studied thoroughly in two isomeric In(III)-isophthalate based MOFs. In-IA-2D-1 is capable of showing proton conductivity (3.4 × 10(-3) S cm(-1)) under humidified conditions (98% RH), whereas In-IA-2D-2 can conduct protons (2.6 × 10(-5) S cm(-1)) under humidified as well as anhydrous conditions.

Solution mediated phase transformation (RHO to SOD) in porous Co-imidazolate based zeolitic frameworks with high water stability.

Here we report a highly porous, water stable Co based ZIF [CoNIm (RHO)] and its solution mediated phase transformation to a less porous and water unstable ZIF [CoNIm (SOD)]. CoNIm (RHO) has high Langmuir surface area [2087 m(2) g(-1)] as well as high water adsorption [200 cm(3) (STP) g(-1)] capacity.

Self-assembled one dimensional functionalized metal-organic nanotubes (MONTs) for proton conduction.

Two self-assembled isostructural functionalized metal-organic nanotubes have been synthesized using 5-triazole isophthalic acid (5-TIA) with In(III) and Cd(II). In- and Cd-5TIA possess one-dimensional (1D) nanotubular architecture and show proton conductivity along regular 1D channels, measured as 5.35 × 10(-5) and 3.61 × 10(-3) S cm(-1) respectively.

Fe(III) complex of biuret-amide based macrocyclic ligand as peroxidase enzyme mimic.

An Fe(III) complex of a biuret-amide based macrocyclic ligand that exhibits both excellent reactivity for the activation of H(2)O(2) and high stability, especially at low pH and high ionic strength, is reported.

Template induced structural isomerism and enhancement of porosity in manganese(II) based metal-organic frameworks (Mn-MOFs).

Three new metal-organic framework isomers have been synthesized by using the organic linker 5-triazole isophthalic acid and Mn(NO(3))(2)·xH(2)O. Structural conversions from non-porous to porous MOFs due to the template effect have been observed. The cross-sectional pore apertures of the resulting Mn-MOFs are comparable to the molecular dimensions of the template (pyrazine and 4,4'-bipyridine). The periodic increased porosity in Mn-MOFs depending on the size of the template used has been further confirmed by the CO(2) adsorption isotherms.

Amino functionalized zeolitic tetrazolate framework (ZTF) with high capacity for storage of carbon dioxide.

A three dimensional -NH(2) functionalized Zeolitic Tetrazolate Framework (ZTF-1) has been reported. The framework adopts a dia topology (M-L-M angle is close to 156°). ZTF-1 shows high CO(2) (273 K) and H(2) (77 K) uptake due to the presence of the free -NH(2) group and uncoordinated tetrazolate nitrogen.