Materials

Photochemistry with Fluorinated Gases Made Practical Using Metal–Organic Frameworks

Context

Fluoroalkyl groups are ubiquitous in pharmaceuticals and agrochemicals, but their installation often relies on heavy, expensive, and poorly atom-efficient reagents. Simple fluorinated gases would be ideal building blocks due to their high fluorine content and low molecular weight, yet their use in photochemistry is limited by safety concerns, poor stoichiometric control, and difficult handling. Existing solutions such as gas balloons or flow reactors either lack precision or require specialized equipment, restricting broad adoption in synthetic laboratories.

What's New

This work introduces a general strategy for performing photochemical fluoroalkylation reactions using fluorinated gases stored inside a robust, redox-innocent metal–organic framework. By adsorbing common fluorinated gases into the aluminum fumarate framework, gaseous reagents are converted into stable, solid materials that can be weighed, stored, and dosed like conventional reagents. These gas–MOF composites enable a wide range of photoinduced transformations, including radical substitutions, metallophotoredox cross-couplings, and cycloadditions, without interfering with the photochemical processes themselves.

Why It Matters

The study removes one of the main practical barriers to using fluorinated gases in photochemistry. By transforming hazardous and difficult-to-handle gases into bench-stable solids, the work enables precise stoichiometric control, improved safety, and compatibility with standard batch reaction setups. This approach opens access to highly atom-economical fluoroalkylation reactions and provides a scalable, sustainable route for late-stage functionalization of complex molecules relevant to medicinal and agrochemical research.

Limitations & Open Questions

While the metal–organic framework platform proves broadly compatible with photochemical reactions, the demonstrated system relies on a specific framework material with carefully balanced stability and pore size. The approach may require optimization or alternative frameworks to accommodate other classes of gaseous reagents or more reactive photochemical conditions. In addition, although long-term storage stability is demonstrated, large-scale industrial deployment would require further evaluation of gas loading, regeneration efficiency, and lifecycle costs of the framework material.
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References

Journal of the American Chemical Society (2026)

DOI: https://doi.org/10.1021/jacs.5c17931

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