Oxygen- and proton-transporting open framework ionomer for medium-temperature fuel cells.

Medium-temperature proton exchange membrane fuel cells (MT PEMFCs) operating at 100° to 120°C have improved kinetics, simplified thermal and water management, and broadened fuel tolerance compared with low-temperature PEMFCs. However, high temperatures lead to Nafion ionomer dehydration and exacerbate gas transportation limitations. Inspired by osmolytes found in hyperthermophiles, we developed α-aminoketone-linked covalent organic framework (COF) ionomers, interwoven with Nafion, to act as "breathable" proton conductors.

Rapid synthesis of aminal-linked covalent organic frameworks for CO/CH separation.

As an emerging category of crystalline porous materials, covalent organic frameworks (COFs) are primarily synthesized solvothermal methods. However, achieving rapid synthesis of COFs through this approach poses a significant challenge. To address the issue of slow synthesis, we studied the crystallization process of aminal-linked COFs the condensation of a cost-effective aldehyde and secondary amine, and successfully expedited the synthesis of COFs within a one-hour duration.

Identification of two-dimensional covalent organic frameworks with topology and their application in photocatalytic hydrogen evolution.

Covalent organic frameworks have attracted considerable attention in recent years as a distinct class of crystalline porous organic materials. Their functional properties are inherently linked to their structural characteristics. Although hundreds of COFs have been reported so far, the types of their topologic structure are still limited.

An Azulene-Based Crystalline Porous Covalent Organic Framework for Efficient Photothermal Conversion.

The designed synthesis of a crystalline azulene-based covalent organic framework (COF-Azu-TP) is presented and its photothermal property is investigated. Azulene, a distinctive 5-7 fused ring non-benzenoid aromatic compound with a large intramolecular dipole moment and unique photophysical characteristics, is introduced as the key feature in COF-Azu-TP. The incorporation of azulene moiety imparts COF-Azu-TP with broad-spectrum light absorption capability and interlayer dipole interactions, which makes COF-Azu-TP a highly efficient photothermal conversion material.

Converting an amorphous covalent organic polymer to a crystalline covalent organic framework mediated by a repairing agent.

We herein report a new approach to converting an amorphous covalent organic polymer to a crystalline heteropore covalent organic framework (COF), which is promoted by using an additive for structure repair. This provides a new method for the construction of COFs from cross-linked polymers.

Syntheses of Covalent Organic Frameworks via a One-Pot Suzuki Coupling and Schiff's Base Reaction for C H /C H Separation.

Covalent organic frameworks (COFs) featuring permanent porosity, designable topologies, and tailorable functionalities have attracted great interest in the past two decades. Developing efficient modular approaches to rationally constructing COFs from a set of molecules via covalent linking has been long pursued. Herein, we report a facile one-pot strategy to prepare COFs via an irreversible Suzuki coupling reaction followed by a reversible Schiff's base reaction without the need for intermediate isolation.

A Facile, Efficient, and General Synthetic Method to Amide-Linked Covalent Organic Frameworks.

Amide-linked covalent organic frameworks (amide COFs) possess enormous potentials in practical applications benefiting from their high stability and polyamide structures. However, they suffer from very limited accessibility. Herein, we report a new linkage conversion method to rapidly synthesize crystalline amide COFs through oxidation of imine linkages in their corresponding imine-linked frameworks with KHSO as an oxidant under very mild conditions.

Materials genomics methods for high-throughput construction of COFs and targeted synthesis.

Materials genomics represents a research mode for materials development, for which reliable methods for efficient materials construction are essential. Here we present a methodology for high-throughput construction of covalent organic frameworks (COFs) based on materials genomics strategy, in which a gene partition method of genetic structural units (GSUs) with reactive sites and quasi-reactive assembly algorithms (QReaxAA) for structure generation were proposed by mimicking the natural growth processes of COFs, leading to a library of 130 GSUs and a database of ~470,000 materials containing structures with 10 unreported topologies as well as the existing COFs. As a proof-of-concept example, two generated 3D-COFs with ffc topology and two 2D-COFs with existing topologies were successfully synthesized.

Synthesis and Reactivity of a Scandium Terminal Hydride: H Activation by a Scandium Terminal Imido Complex.

Dihydrogen is easily activated by a scandium terminal imido complex containing the weakly coordinated THF. The reaction proceeds through a 1,2-addition mechanism, which is distinct from the σ-bond metathesis mechanism reported to date for rare-earth metal-mediated H activation. This reaction yields a scandium terminal hydride, which is structurally well-characterized, being the first one to date.

Lewis acid triggered reactivity of a Lewis base stabilized scandium-terminal imido complex: C-H bond activation, cycloaddition, and dehydrofluorination.

A stable scandium-terminal imido complex is activated by borane to form an unsaturated terminal imido complex by removing the coordinated Lewis base, 4-(dimethylamino)pyridine, from the metal center. The ensuing terminal imido intermediate can exist as a THF adduct and/or undergo cycloaddition reaction with an internal alkyne, C-H activation of a terminal alkene, and dehydrofluorination of fluoro-substituted benzenes or alkanes at room temperature. DFT investigations further highlight the ease of C-H activation for terminal alkene and fluoroarene.