Photochemistry of Hypervalent Iodoazide Derivatives

Gupta, Nikita; Zhu, Haoran; O’Shea, Joseph M.; Ayitou, Anoklase jean-Luc; Hemley, Russell J.; Driver, Tom G.; Glusac, Ksenija D.

doi:10.1021/acs.jpca.5c02567

Photochemistry of Hypervalent Iodoazide Derivatives

Journal Article · Tue Jun 17 04:00:00 EDT 2025 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5c02567· OSTI ID:2574007

Gupta, Nikita ^[1]; Zhu, Haoran ^[2]; O’Shea, Joseph M. ^[2]; ^[2]; ^[2]; ^[2]; ^[1]

Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Univ. of Illinois, Chicago, IL (United States)

The photochemical properties and reaction mechanisms of a series of hypervalent iodoazide compounds (R–IN3) were investigated, with substituents (−CH₃, −H, −CF₃) tuning the electronic density of the phenyl ring. With the help of UV irradiation, ultrafast time-resolved spectroscopy, and density functional theory (DFT) calculations, we elucidated the mechanisms of azide radical (N₃^•) release and its subsequent reactivity. UV–vis spectroscopy reveals that the photoconversion rates follow the trend CH3 > H > CF3, aligning with DFT-calculated ΔG values for ring-opening transitions. Homolytic cleavage of the I–N bond is identified as the dominant pathway for N3• generation upon UV irradiation, occurring within 400 fs. The released azide radicals react with the solvent molecules, while the iodo radical R–I_C^• fragments undergo a thermodynamically uphill lactone ring-opening (RO) reaction and subsequent hydrogen atom abstraction from the solvent to form carboxylic acids R–I–COOH, as validated by NMR and IR spectroscopy. The study also highlights the role of substituents in influencing reaction kinetics and intermediate stability, with electron-donating groups accelerating the release of the N₃^• species. This work bridges experimental observations with computational predictions, offering a foundation for future advancements in azide-based reactions and materials.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); US Army Research Office (ARO)

Grant/Contract Number:: NA0004153

OSTI ID:: 2574007

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 31 Vol. 129; ISSN 1089-5639; ISSN 1520-5215

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

azides
bond cleavage
irradiation
solvents
substituents

Photochemistry of Hypervalent Iodoazide Derivatives

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