Isolation of a Terminal Cobalt Nitride in a Metal–Organic Framework

Transition metal nitrides are reactive intermediates in biological and industrial processes. Chemists have synthesized molecular model complexes of such reactive species to understand their function and electronic requirements for new applications. However, molecular chemistry can suffer from intra- and intermolecular decomposition pathways, which preclude further discovery of unknown reactive species. Metal-organic frameworks offer an opportunity for creating long-lived forms of such species with the vacuum of the pore suppressing degradation while simultaneously enabling substrate access for controlled reactivity studies. Here, we report the characterization of an elusive terminal cobalt nitride species generated through photolysis or thermolysis of a site-isolated cobalt azide within the evacuated metal-organic framework CoN<sub>3</sub>-MFU-4<i>l</i>. The first crystal structure of such a species is presented, with vibrational, X-ray absorption, and electron paramagnetic resonance spectroscopies providing further direct evidence for its formation while elucidating its electronic structure. The system additionally enables subsequent reactivity studies with selected substrates, revealing a unique ambiphilic behavior for a metal nitride species.

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Publication Details

Journal
Journal of the American Chemical Society
Published
2025-12-22
DOI
https://doi.org/10.1021/jacs.5c16444
Primary Topic
Metal-Organic Frameworks: Synthesis and Applications
Type
article
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article

Isolation of a Terminal Cobalt Nitride in a Metal–Organic Framework

Danh X. Ngo, Khetpakorn Chakarawet, J. Urban, Patrick W. Smith et al.
Journal of the American Chemical Society
Metal-Organic Frameworks: Synthesis and Applications
article

Isolation of a Terminal Cobalt Nitride in a Metal–Organic Framework

Danh X. Ngo, Khetpakorn Chakarawet, J. Urban, Patrick W. Smith, Brandon R. Barnett, Edward I. Solomon, Mauricio Lopez Luna, Monika Blum, Ryan A. Klein, Zikri Hasanbasri, Jordan W. Taylor, Nicole Removski, Jeffrey A. Reimer, Ying-Pin Chen, Jonas Börgel, Alexander J. Heyer, Tieyan Chang, Nykita Z. Rustad, Henry Z. H. Jiang, Stefan G. Minasian, Chaochao Dun, Vincent R. Allen, R. David Britt, Wanli Yang, Yu-Sheng Chen, N. Isaac Zakaria, Maria V. Paley, Jeffrey R. Long, T. David Harris
article en

Abstract

Transition metal nitrides are reactive intermediates in biological and industrial processes. Chemists have synthesized molecular model complexes of such reactive species to understand their function and electronic requirements for new applications. However, molecular chemistry can suffer from intra- and intermolecular decomposition pathways, which preclude further discovery of unknown reactive species. Metal-organic frameworks offer an opportunity for creating long-lived forms of such species with the vacuum of the pore suppressing degradation while simultaneously enabling substrate access for controlled reactivity studies. Here, we report the characterization of an elusive terminal cobalt nitride species generated through photolysis or thermolysis of a site-isolated cobalt azide within the evacuated metal-organic framework CoN<sub>3</sub>-MFU-4<i>l</i>. The first crystal structure of such a species is presented, with vibrational, X-ray absorption, and electron paramagnetic resonance spectroscopies providing further direct evidence for its formation while elucidating its electronic structure. The system additionally enables subsequent reactivity studies with selected substrates, revealing a unique ambiphilic behavior for a metal nitride species.

Journal of the American Chemical SocietyVol. 148(1)
Argonne National Laboratory (US), National Institute of Standards and Technology (US), University of Nevada, Reno (US), Lawrence Berkeley National Laboratory (US), University of California System (US), National Institute of Standards (EG), NOAA Chemical Sciences Laboratory (US), Foundry (United Kingdom) (GB), Institute for Nuclear Research (UA), Advanced Photonix (United States) (US), Advanced Light Source, Molecular Foundry, Advanced Photon Source, Stanford University (US)
Openalex Percentile: Top 45%
Metal-Organic Frameworks: Synthesis and Applications
DOISourceOpenAlex
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