Enolate carboxylation by CO2 is essential to applications ranging from polymer synthesis to CO2 capture, yet the CO2 reactivity of stabilized enolates, such as β-dicarbonyl enolates, remains understud...

Recipients are recognized for significant contributions to chemistry and the chemistry community

Hydrogen atom transfer (HAT) mediated by halogen radicals represents a powerful approach for the functionalization of inert C(sp3)–H bonds. Chlorine radical (Cl•), for example, is capable of generatin...

Photochemistry has greatly advanced the sustainable synthesis of complex molecules, but its application for late-stage fluoroalkylation─crucial due to the presence of fluorine in >20% of pharmaceuticals and >65% of agrochemicals─is hindered by the poor atom economy of traditional fluoroalkylating agents. Herein, we demonstrate that simple fluorinated gases, which represent ideal building blocks for fluorochemical synthesis, can be stored within the robust, inexpensive, and redox-innocent metal–organic framework Al–fum to streamline the development of 11 photoinduced fluoroalkylation reactions, including bimolecular homolytic substitution (SH2), metallophotoredox cross-coupling, and [2+2] cycloaddition reactions. The gas–Al–fum reagents are prepared via simple gas-dosing procedures, stable for several months in a desiccator at room temperature, and are compatible with reaction optimization campaigns and mechanistic studies using precise quantities of gases. Overall, our findings provide a general platform for the utilization of inexpensive gaseous building blocks in photochemistry, paving the way for the sustainable synthesis of next-generation fluorochemicals.

Enolate carboxylation by CO2 is essential to applications ranging from polymer synthesis to CO2 capture, yet the CO2-reactivity of stabilized enolates, such as β-dicarbonyl enolates, remains understud...

Susumu Kitagawa, Richard Robson and Omar M. Yaghi win the prize for developing metal–organic frameworks

Understanding dynamic catalyst evolution, particularly Cu-based single-atom catalysts, faces tremendous challenges of tracking rapid and nanoscale evolution and uncontrolled catalyst reoxidation durin...

The combination of electricity and light can provide a sustainable route to drive challenging synthetic transformations, but current catalysts are plagued by poor stability and mechanistic ambiguity. ...

N-vinyl azoles are prevalent moieties in pharmaceuticals, and fluorovinyl groups are widely recognized as carbonyl bioisosteres in drug design. Thus, N-fluorovinylated heteroarenes represent highly de...

The winners are being acknowledged for their outstanding achievements in chemistry across various fields in the discipline

Nature Chemistry - The combination of electricity and light can provide a sustainable route to drive challenging synthetic transformations, but current catalysts are plagued by poor stability and...

A grant from the Ono Pharma Breakthrough Science Initiative, which supports bold new ideas in science, will help Cornell researchers study how chemical modifications to proteins play a powerful role i...

Graduate Field Coordinator-Department of Chemistry and Chemical Biology The Opportunity The Department of Chemistry and Chemical Biology is seeking a dedicated and detail-oriented Graduate Field Coord...

Public Access Policy | Data Sharing - Learn about NIH data sharing policies and how to share and access scientific data

Nature Energy - Amine oxides step up

A major drawback to the implementation of metal–organic frameworks (MOFs) on scale is the vast quantity of organic solvents, typically N,N-dimethylformamide (DMF), required to synthesize even small qu...

Nature Communications - Structural dynamics play an essential role in enzymatic catalysis. Here, the authors use cryo-EM to reveal the conformational landscapes of a class I ribonucleotide...

Hydrofluorocarbons (HFCs) are anthropogenically produced greenhouse gases with longer atmospheric lifetimes and higher global warming potentials than those of carbon dioxide. General strategies to abate their emissions from industrial point sources, such as via adsorptive capture, remain scarce. Herein, we uncover the key structure–property relationships that lead to strong binding of HFCs such as fluoroform (CHF3) and difluoromethane (CH2F2) in metal–organic frameworks (MOFs) under the low pressures relevant to flue gas scrubbing. Extensive gas sorption and computational studies support that the Zr-based microporous framework MOF-801-Br or HHU-2-Br (HHU = Heinrich-Heine-University Düsseldorf) strongly binds HFCs due to its synergistic combination of Zr-OH sites on the nodes and bromine sites on the linkers. As such, MOF-801-Br demonstrates a record-setting performance for separating CHF3 from N2 under dilute conditions. Our work highlights that the combination of multiple hydrogen-bonding sites in microporous MOFs represents a generalizable strategy for HFC capture, enabling their selective removal from industrial waste streams.

Degradable thermoset multimaterials can be synthesized from a commercially accessible, biosourced monomer using orthogonal polymerizations in a single pot; after selective degredation, the resulting s...

The synthesis of amides from amines and carboxylic acids is the most widely carried out reaction in medicinal chemistry. Yet, most amide couplings are still conducted using stoichiometric reagents, le...