Linker Conformation Controls Oxidation Potentials and Electrochromism in Highly Stable Zr-Based Metal-Organic Frameworks.

The development of tailor-made electrochromic (EC) materials requires a large variety of available substances with properties that precisely match the task. Since the inception of electrochromic metal-organic frameworks (MOFs), the field relies only on a limited set of building blocks, providing the desired electrochromic effect. Herein, we demonstrate for the first time the implementation of a Piccard-type system (N,N,N',N'-benzidinetetrabenzoate) into Zr-MOFs to obtain electrochromic materials. With fast switching rates, high contrast ratio, long-life stability, and exceptional chemical and physical stability, the novel material is on par with inorganic EC material. The new EC system exhibits an ultrahigh contrast from the bleaching state, with transmittance in the visible region >53%, to the colored state with a transmittance of ca. 3%. The 5 µm thick film attained up to 90% of the coloring in 12.5 s and exhibited high electrochemical reversibility. Moreover, the conformational lability of the electrochromic ligand chosen is locked via the topology design of the framework, which is not attainable in the solution. Locked conformations of the redox active linker in distinct polymorphous frameworks (DUT-65 and DUT-66) feature different redox characteristics and opens the door to the overarching control of the oxidation pathway in the Piccard-type systems.

An Alkyne-Bridged Covalent Organic Framework Featuring Interactive Pockets for Bromine Capture.

The high degree of corrosivity and reactivity of bromine, which is released from various sources, poses a serious threat to the environment. Moreover, its coexistence with iodine forming an equilibrium compound, iodine monobromide (IBr) necessitates the selective capture of bromine from halogen mixtures. The electrophilicity of halogens to π-electron rich structures enabled us to strategically design a covalent organic framework for halogen capture, featuring a defined pore environment with localized sorption sites. The higher capture capacity of bromine (4.6 g g-1) over iodine by ~41 % shows its potential in selective capture. Spectroscopic results uncovering the preferential interaction sites are supported by theoretical investigations. The alkyne bridge is a core functionality promoting the selectivity in capture by synergistic physisorption, rationalized by the higher orbital overlap of bromine due to its smaller atomic size as well as reversible chemical interactions. The slip stacking in the structure has further promoted this phenomenon by creating clusters of molecular interaction sites with bromine intercalated between the layers. The inclusion of unsaturated moieties, i.e. triple bonds and the complementary pore geometry offer a promising design strategy for the construction of porous materials for halogen capture.

Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium-Sulfur Battery Cathodes.

Dithiine linkage formation via a dynamic and self-correcting nucleophilic aromatic substitution reaction enables the de novo synthesis of a porous thianthrene-based two-dimensional covalent organic framework (COF). For the first time, this organo-sulfur moiety is integrated as a structural building block into a crystalline layered COF. The structure of the new material deviates from the typical planar interlayer π-stacking of the COF to form undulated layers caused by bending along the C-S-C bridge, without loss of aromaticity and crystallinity of the overall COF structure. Comprehensive experimental and theoretical investigations of the COF and a model compound, featuring the thianthrene moiety, suggest partial delocalization of sulfur lone pair electrons over the aromatic backbone of the COF decreasing the band gap and promoting redox activity. Postsynthetic sulfurization allows for direct covalent attachment of polysulfides to the carbon backbone of the framework to afford a molecular-designed cathode material for lithium-sulfur (Li-S) batteries with a minimized polysulfide shuttle. The fabricated coin cell delivers nearly 77% of the initial capacity even after 500 charge-discharge cycles at 500 mA/g current density. This novel sulfur linkage in COF chemistry is an ideal structural motif for designing model materials for studying advanced electrode materials for Li-S batteries on a molecular level.

Chemically Stable Carbazole-Based Imine Covalent Organic Frameworks with Acidochromic Response for Humidity Control Applications.

Isoreticular chemically stable two-dimensional imine covalent organic frameworks (COFs), further denoted as DUT-175 and DUT-176, are obtained in a reaction of 4,4'-bis(9H-carbazol-9-yl)biphenyl tetraaldehyde with phenyldiamine and benzidine. The crystal structures, solved and refined from the powder X-ray diffraction data and confirmed by high-resolution transmission electron microscopy, indicate AA-stacked layer structures. Both structures feature distorted hexagonal channel pores, assuring remarkable porosity (SBET = 1071 m2 g-1 for DUT-175 and SBET = 1062 m2 g-1 for DUT-176), as confirmed by adsorption of gases and vapors. The complex conjugated π system of the COFs involves electron-rich carbazole building units, which in combination with the imine groups allow reversible pH-dependent protonation of the frameworks, accompanied by charge transfer and shift of the absorption bands in the UV-vis spectrum. The sigmoidal shape of the water vapor adsorption and desorption isotherms with a steep adsorption step at p/p0 = 0.4-0.6 in combination with excellent stability over dozens of adsorption and desorption cycles ranks these COFs among the best materials for indoor humidity control applications.

Overcoming Crystallinity Limitations of Aluminium Metal-Organic Frameworks by Oxalic Acid Modulated Synthesis.

A modulated synthesis approach based on the chelating properties of oxalic acid (H2 C2 O4 ) is presented as a robust and versatile method to achieve highly crystalline Al-based metal-organic frameworks. A comparative study on this method and the already established modulation by hydrofluoric acid was conducted using MIL-53 as test system. The superior performance of oxalic acid modulation in terms of crystallinity and absence of undesired impurities is explained by assessing the coordination modes of the two modulators and the structural features of the product. The validity of our approach was confirmed for a diverse set of Al-MOFs, namely X-MIL-53 (X=OH, CH3 O, Br, NO2 ), CAU-10, MIL-69, and Al(OH)ndc (ndc=1,4-naphtalenedicarboxylate), highlighting the potential benefits of extending the use of this modulator to other coordination materials.

A Precursor-Derived Ultramicroporous Carbon for Printing Iontronic Logic Gates and Super-Varactors.

A liquid precursor for 3D printing ultramicroporous carbons (pore width <0.7 nm) to create a novel in-plane capacitive-analog of semiconductor-based diodes (CAPodes) is presented. This proof-of-concept integrates functional EDLCs into microstructured iontronic devices. The working principle is based on selective ion-sieving, controlling the size of the electrolyte ions, and the nanoporous sieving carbon's pore size. By blocking bulky electrolyte ions from entering the sub-nanometer pores, a unidirectional charging characteristic with controllable ion flux is achieved, leading to diodic U-I characteristics with a high rectification ratio. The liquid precursor approach enables successful printing of miniaturized in-plane CAPodes. A combination of inkjet and extrusion printing techniques with suitable inks is explored to fabricate electrode materials with engineered porosity. Deliberate fine-tuning of the ultramicroporous carbon's porosity and surface area is achieved using a customized carbon precursor and CO2 etching techniques. Electrochemical evaluation of the printed CAPodes demonstrates successful miniaturization compared with macroscopic film assembly. 3D manufacturing and miniaturization allow for the integration of CAPodes into logic gate circuits (OR, AND). For the first time, these switchable devices are used as variable capacitors in a high-pass filter application, adjusting the cut-off frequency of applied alternating voltage analogous to an I-MOS varactor.

Confined Water Cluster Formation in Water Harvesting by Metal-Organic Frameworks: CAU-10-H versus CAU-10-CH3.

Several metal-organic frameworks (MOFs) excel in harvesting water from the air or as heat pumps as they show a steep increase in water uptake at 10-30 % relative humidity (RH%). A precise understanding of which structural characteristics govern such behavior is lacking. Herein, CAU-10-H and CAU-10-CH3 are studied with H, CH3 corresponding to the functions grafted to the organic linker. CAU-10-H shows a steep water uptake ≈18 RH% of interest for water harvesting, yet the subtle replacement of H by CH3 in the organic linker drastically changes the water adsorption behavior to less steep water uptake at much higher humidity values. The materials' structural deformation and water ordering during adsorption with in situ sum-frequency generation, in situ X-ray diffraction, and molecular simulations are unraveled. In CAU-10-H, an energetically favorable water cluster is formed in the hydrophobic pore, tethered via H-bonds to the framework µï£¿OH groups, while for CAU-10-CH3, such a favorable cluster cannot form. By relating the findings to the features of water adsorption isotherms of a series of MOFs, it is concluded that favorable water adsorption occurs when sites of intermediate hydrophilicity are present in a hydrophobic structure, and the formation of energetically favorable water clusters is possible.

Integration of Triphenylene-Based Conductive Metal-Organic Frameworks into Carbon Nanotube Electrodes for Boosting Nonenzymatic Glucose Sensing.

The rational design and preparation of conductive metal-organic frameworks (MOFs) are alluring and challenging pathways to develop active catalysts toward electrocatalytic glucose oxidation. The hybridization of conductive MOFs with carbon nanotubes (CNTs) in the form of a composite can greatly improve the electrocatalytic performance. Herein, a facile one-step synthetic strategy is utilized to fabricate a Ni3(HHTP)2/CNT (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) composite for nonenzymatic detection of glucose in an alkaline solution. The Ni3(HHTP)2/CNT composite, as an electrochemical glucose sensor material, exhibits superior electrocatalytic activity toward glucose oxidation with a wide detection range of up to 3.9 mM, a low detection limit of 4.1 µM (signal/noise = 3), a fast amperometric response time of <2 s, and a high sensitivity of 4774 µA mM-1 cm-2, surpassing the performance of some recently reported nonenzymatic transition-metal-based glucose sensors. In addition, the composite sensor also shows outstanding selectivity, robust long-term electrochemical stability, favorable anti-interference properties, and good reproducibility. This work displays the effectiveness of enhancing the electrocatalytic performance toward glucose detection by combing conductive MOFs with CNTs, thereby opening up an applicable and encouraging approach for the design of advanced nonenzymatic glucose sensors.

Sulfide-Bridged Covalent Quinoxaline Frameworks for Lithium-Organosulfide Batteries.

The chelating ability of quinoxaline cores and the redox activity of organosulfide bridges in layered covalent organic frameworks (COFs) offer dual active sites for reversible lithium (Li)-storage. The designed COFs combining these properties feature disulfide and polysulfide-bridged networks showcasing an intriguing Li-storage mechanism, which can be considered as a lithium-organosulfide (Li-OrS) battery. The experimental-computational elucidation of three quinoxaline COFs containing systematically enhanced sulfur atoms in sulfide bridging demonstrates fast kinetics during Li interactions with the quinoxaline core. Meanwhile, bilateral covalent bonding of sulfide bridges to the quinoxaline core enables a redox-mediated reversible cleavage of the sulfursulfur bond and the formation of covalently anchored lithium-sulfide chains or clusters during Li-interactions, accompanied by a marked reduction of Li-polysulfide (Li-PS) dissolution into the electrolyte, a frequent drawback of lithium-sulfur (Li-S) batteries. The electrochemical behavior of model compounds mimicking the sulfide linkages of the COFs and operando Raman studies on the framework structure unravels the reversibility of the profound Li-ion-organosulfide interactions. Thus, integrating redox-active organic-framework materials with covalently anchored sulfides enables a stable Li-OrS battery mechanism which shows benefits over a typical Li-S battery.

Solid-state NMR insights into alcohol adsorption by metal-organic frameworks: adsorption state, selectivity, and adsorption-induced phase transitions.

Alcohol adsorption by metal-organic frameworks (ZIF-8 and ZIF-11) in aqueous solutions is investigated including alcohol mixtures. Solid-state 13C NMR spectroscopy is demonstrated to be well-suited for such liquid-phase adsorption studies at the molecular level. Adsorption-induced immobilization could be visualized. Finally, an unexpected phase transition of ZIF-11 was discovered.