Computational Exploration of Adsorption-Based Hydrogen Storage in Mg-Alkoxide Functionalized Covalent-Organic Frameworks (COFs): Force-Field and Machine Learning Models.

Hydrogen is a clean-burning fuel that can be converted to other forms. of energy without generating any greenhouse gases. Currently, hydrogen is stored either by compression to high pressure (>700 bar) or cryogenic cooling to liquid form (<23 K).

Polymer Hosts Containing Carbazole-Dibenzothiophene-Based Pendants for Application in High-Performance Solution-Processed TADF-OLEDs.

The film-forming capability of the host plays a crucial role in effectively forming a light-emitting layer through a solution process in organic light-emitting diodes (OLEDs). In this study, we synthesized two side-chain polymer hosts, and , consisting of carbazole and dibenzothiophene. The synthesis was carried out through radical polymerization using styrene-based host monomers.

Tailored Postsynthetic Nitration of a Hypercrosslinked Polymer for Single-Step Ethylene Purification from a Ternary C Gas Mixture.

Purifying CH from a ternary CH/CH/CH mixture poses a substantial industrial challenge due to their close physical and chemical properties. In this study, we introduce an innovative design approach to regulate and optimize the nitration degree of a hypercrosslinked polymer to achieve targeted separation performance. We synthesized a porous organic polymer (HCP) using the solvent knitting method and carried out its postsynthetic nitration, resulting in HCP-NO-1 and HCP-NO-2 with different nitration degrees.

Extended MOF-74-Type Variant with an Azine Linkage: Efficient Direct Air Capture and One-Pot Synthesis.

Direct air capture (DAC) shows considerable promise for the effective removal of CO; however, materials applicable to DAC are lacking. Among metal-organic framework (MOF) adsorbents, diamine-Mg(dobpdc) (dobpdc = 4,4-dioxidobiphenyl-3,3'-dicarboxylate) effectively removes low-pressure CO, but the synthesis of the organic ligand requires high temperature, high pressure, and a toxic solvent. Besides, it is necessary to isolate the ligand for utilization in the synthesis of the framework.

High Hydrogen Storage in Trigonal Prismatic Monomer-Based Highly Porous Aromatic Frameworks.

Hydrogen storage is crucial in the shift toward a carbon-neutral society, where hydrogen serves as a pivotal renewable energy source. Utilizing porous materials can provide an efficient hydrogen storage solution, reducing tank pressures to manageable levels and circumventing the energy-intensive and costly current technological infrastructure. Herein, two highly porous aromatic frameworks (PAFs), C-PAF and Si-PAF, prepared through a Yamamoto C─C coupling reaction between trigonal prismatic monomers, are reported.

Precision-Engineered Medium-Sized Molecular Host and Emitter for Ensuring Consistent Performance in Solution-Processed Narrowband OLEDs.

In this study, two novel multiple resonance (MR) emitters, DtCzBN and Cy-DtCzBN, were designed based on the well-known BCzBN structure and synthesized for narrowband solution-processed organic light-emitting diodes (OLEDs). Cy-DtCzBN possesses a dimeric V-shaped structure formed by coupling two individual DtCzBN units via a nonconjugated cyclohexane linker. When compared with DtCzBN, Cy-DtCzBN, as a medium-sized molecule, was found to maintain the optical and photophysical properties of the corresponding monomeric unit, DtCzBN, but exhibits high thermal stability, excellent solubility, and good film-forming ability.

Postsynthetically Modified Alkoxide-Exchanged Ni(OR)BTDD: Synergistic Interactions of CO with Open Metal Sites and Functional Groups.

Postsynthetic modifications (PSMs) of metal-organic frameworks (MOFs) play a crucial role in enhancing material performance through open metal site (OMS) functionalization or ligand exchange. However, a significant challenge persists in preserving open metal sites during ligand exchange, as these sites are inherently bound by incoming ligands. In this study, for the first time, we introduced alkoxides by exchanging bridging chloride in NiClBTDD (BTDD=bis (1H-1,2,3,-triazolo [4,5-b],-[4',5'-i]) dibenzo[1,4]dioxin) through PSM.

Solvent-Driven Dynamics: Crafting Tailored Transformations of Cu(II)-Based MOFs.

Metal-organic frameworks (MOFs), a sort of crystalline porous coordination polymers composed of metal ions and organic linkers, have been intensively studied for their ability to take up nonpolar gas-phase molecules such as ethane and ethylene. In this context, interpenetrated MOFs, where multiple framework nets are entwined, have been considered promising materials for capturing nonpolar molecules due to their relatively higher stability and smaller micropores. This study explores a solvent-assisted reversible strategy to interpenetrate and deinterpenetrate a Cu(II)-based MOF, namely, MOF-143 (noninterpenetrated form) and MOF-14 (doubly interpenetrated forms).

Boc Protection for Diamine-Appended MOF Adsorbents to Enhance CO Recyclability under Realistic Humid Conditions.

Among the various metal-organic framework (MOF) adsorbents, diamine-functionalized Mg(dobpdc) (dobpdc = 4,4-dioxidobiphenyl-3,3'-dicarboxylate) shows remarkable carbon dioxide removal performance. However, applying diamine-functionalized Mg(dobpdc) in practical applications is premature because it shows persistent performance degradation under real flue gas conditions containing water vapor owing to diamine loss during wet cycles. To address this issue, we employed hydrophobic carbonate compounds to protect diamine groups in een-Mg(dobpdc) (, een = N-ethylethylenediamine).

Porous organic materials for iodine adsorption.

The nuclear industry will continue to develop rapidly and produce energy in the foreseeable future; however, it presents unique challenges regarding the disposal of released waste radionuclides because of their volatility and long half-life. The release of radioactive isotopes of iodine from uranium fission reactions is a challenge. Although various adsorbents have been explored for the uptake of iodine, there is still interest in novel adsorbents.

Aminal-Linked Covalent Organic Frameworks with hxl-a and Quasi-hcb Topologies for Efficient C H /C H Separation.

In reticular chemistry, topology is a powerful concept for defining the structures of covalent organic frameworks (COFs). However, due to the lack of diversity in the symmetry and reaction stoichiometry of the monomers, only 5% of the two-dimensional topologies have been reported to be COFs. To overcome the limitations of COF connectivity and pursue novel topologies in COF structures, two aminal-linked COFs, KUF-2 and KUF-3, are prepared, with dumbbell-shaped secondary building units.

Switchable Xe/Kr Selectivity in a Hofmann-Type Metal-Organic Framework via Temperature-Responsive Rotational Dynamics.

The development of adsorbents for Kr and Xe separation is essential to meet industrial demands and for energy conservation. Although a number of previous studies have focused on Xe-selective adsorbents, stimuli-responsive Xe/Kr-selective adsorbents still remain underdeveloped. Herein, a Hofmann-type framework Co(DABCO)[Ni(CN) ] (referred to as CoNi-DAB; DABCO = 1,4-diazabicyclo[2,2,2]octane) that provides a temperature-dependent switchable Xe/Kr separation performance is reported.

Wavelength engineerable porous organic polymer photosensitizers with protonation triggered ROS generation.

Engineering excitation wavelength of photosensitizers (PSs) for enhanced reactive oxygen species (ROS) generation has inspired new windows for opportunities, enabling investigation of previously impracticable biomedical and photocatalytic applications. However, controlling the wavelength corresponding to operating conditions remains challenging while maintaining high ROS generation. To address this challenge, we implement a wavelength-engineerable imidazolium-based porous organic photocatalytic ROS generation system (KUP system) via a cost-effective one-pot reaction.

Electronic Effect-Modulated Enhancements of Proton Conductivity in Porous Organic Polymers.

We proposed a new strategy to maximize the density of acidic groups by modulating the electronic effects of the substituents for high-performance proton conductors. The conductivity of the sulfonated 1-MeL40-S with methyl group corresponds to 2.29×10  S cm at 80 °C and 90 % relative humidity, remarkably an 22100-fold enhancement over the nonsulfonated 1-MeL40.

Protocol for the fabrication of porous organic polymer-based composites for photocatalytic degradation of a sulfur mustard simulant.

Although porous organic polymer (POP) has been explored as a promising photosensitizer, its powdered form makes it unfavorable for practical applications. Here, we demonstrate a protocol for fabricating imidazoline-based POP composites using fabric and sponge as substrates. This fabrication is limited to POPs with aldehyde containing organic building blocks.

Correction: Post-synthetic modifications in porous organic polymers for biomedical and related applications.

Correction for 'Post-synthetic modifications in porous organic polymers for biomedical and related applications' by Ji Hyeon Kim , , 2022, , 43-56, https://doi.org/10.1039/D1CS00804H.

Functionalization of Diamine-Appended MOF-Based Adsorbents by Ring Opening of Epoxide: Long-Term Stability and CO Recyclability under Humid Conditions.

Although diamine-appended metal-organic framework (MOF) adsorbents exhibit excellent CO adsorption performance, a continuous decrease in long-term capacity during repeated wet cycles remains a formidable challenge for practical applications. Herein, we present the fabrication of diamine-appended Mg(dobpdc)-alumina beads (-; een = -ethylethylenediamine; = number of carbon atoms attached to epoxide) coated with hydrophobic silanes and alkyl epoxides. The reaction of epoxides with diamines in the portal of the pore afforded sufficient hydrophobicity, hindered the penetration of water vapor into the pores, and rendered the modified diamines less volatile.

High Gravimetric and Volumetric Ammonia Capacities in Robust Metal-Organic Frameworks Prepared via Double Postsynthetic Modification.

Ammonia is a promising energy vector that can store the high energy density of hydrogen. For this reason, numerous adsorbents have been investigated as ammonia storage materials, but ammonia adsorbents with a high gravimetric/volumetric ammonia capacity that can be simultaneously regenerated in an energy-efficient manner remain underdeveloped, which hampers their practical implementation. Herein, we report Ni_acryl_TMA (TMA = thiomallic acid), an acidic group-functionalized metal-organic framework prepared via successive postsynthetic modifications of mesoporous NiClBTDD (BTDD = bis(1-1,2,3,-triazolo [4,5-],-[4',5'-]) dibenzo[1,4]dioxin).

Reversible ammonia uptake at room temperature in a robust and tunable metal-organic framework.

Ammonia is useful for the production of fertilizers and chemicals for modern technology, but its high toxicity and corrosiveness are harmful to the environment and human health. Here, we report the recyclable and tunable ammonia adsorption using a robust imidazolium-based MOF (JCM-1) that uptakes 5.7 mmol g of NH at 298 K reversibly without structural deformation.

Post-synthetic modifications in porous organic polymers for biomedical and related applications.

Porous organic polymers (POPs) are prepared by crosslinked polymerization of multidimensional rigid aromatic building blocks. Generally, POPs can be classified into crystalline covalent organic frameworks (COFs) and other poorly crystalline or amorphous porous polymers. Due to their remarkable intrinsic properties, such as high porosity, stability, tunability, and presence of numerous building blocks, several new POPs are being developed for application across various scientific fields.

Diamine Functionalization of a Metal-Organic Framework by Exploiting Solvent Polarity for Enhanced CO Adsorption.

Diamine-appended metal-organic frameworks (MOFs) exhibit exceptional CO adsorption capacities over a wide pressure range because of the strong interaction between basic amine groups and acidic CO. Given that their high CO working capacity is governed by solvent used during amine functionalization, a systematic investigation on solvent effect is essential but not yet demonstrated. Herein, we report a facile one-step solvent exchange route for the diamine functionalization of MOFs with open metal sites, using an efficient method to maximize diamine loading.