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1. Photolysis of 3‐Azido‐3‐phenyl‐3 H ‐isobenzofuran‐1‐one at Ambient and Cryogenic Temperatures ^†

   https://doi.org/10.1111/php.13500  

   Thenna‐Hewa, Kosala; Sebastien, William; Lemen, Elaine M.; Karney, William L.; Abe, Manabu; Gudmundsdottir, Anna D. (August 2021, Photochemistry and Photobiology)

   Abstract Although alkyl azides are known to typically form imines under direct irradiation, the product formation mechanism remains ambiguous as some alkyl azides also yield the corresponding triplet alkylnitrenes at cryogenic temperatures. The photoreactivity of 3‐azido‐3‐phenyl‐3H‐isobenzofuran‐1‐one (1) was investigated in solution and in cryogenic matrices. Irradiation (λ = 254 nm) of azide 1 in acetonitrile yielded a mixture of imines 2 and 3. Monitoring of the reaction progress using UV‐Vis absorption spectroscopy revealed an isosbestic point at 210 nm, indicating that the reaction proceeded cleanly. Similar results were observed for the photoreactivity of azide 1 in a frozen 2‐methyltetrahydrofuran (mTHF) matrix. Irradiation of azide 1 in an argon matrix at 6 K resulted in the disappearance of its IR bands with the concurrent appearance of IR bands corresponding to imines 2 and 3. Thus, it was theorized that azide 1 forms imines 2 and 3 via a concerted mechanism from its singlet excited state or through singlet alkylnitrene¹1N, which does not intersystem cross to its triplet configuration. This proposal was supported by CASPT2 calculations on a model system, which suggested that the energy gap between the singlet and triplet configurations of alkylnitrene 1N is 33 kcal/mol, thus making intersystem crossing inefficient. 

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2. Heavy‐Atom Tunneling Through Crossing Potential Energy Surfaces: Cyclization of a Triplet 2‐Formylarylnitrene to a Singlet 2,1‐Benzisoxazole

   https://doi.org/10.1002/anie.202006640  

   Nunes, Cláudio M.; Viegas, Luís P.; Wood, Samuel A.; Roque, José P. L.; McMahon, Robert J.; Fausto, Rui (August 2020, Angewandte Chemie International Edition)

   Abstract Not long ago, the occurrence of quantum mechanical tunneling (QMT) chemistry involving atoms heavier than hydrogen was considered unreasonable. Contributing to the shift of this paradigm, we present here the discovery of a new and distinct heavy‐atom QMT reaction. Triplet syn‐2‐formyl‐3‐fluorophenylnitrene, generated in argon matrices by UV‐irradiation of an azide precursor, was found to spontaneously cyclize to singlet 4‐fluoro‐2,1‐benzisoxazole. Monitoring the transformation by IR spectroscopy, temperature‐independent rate constants (k≈1.4×10⁻³ s⁻¹; half‐life of ≈8 min) were measured from 10 to 20 K. Computational estimated rate constants are in fair agreement with experimental values, providing evidence for a mechanism involving heavy‐atom QMT through crossing triplet to singlet potential energy surfaces. Moreover, the heavy‐atom QMT takes place with considerable displacement of the oxygen atom, which establishes a new limit for the heavier atom involved in a QMT reaction in cryogenic matrices. 

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3. Improved computational modeling of the kinetics of the acetylperoxy + HO ₂ reaction

   https://doi.org/10.1039/d2fd00030j  

   Kuwata, Keith T.; DeVault, Marla P.; Claypool, Duncan J. (October 2022, Faraday Discussions)

   The acetylperoxy + HO 2 reaction has multiple impacts on the troposphere, with a triplet pathway leading to peracetic acid + O 2 (reaction (1a)) competing with singlet pathways leading to acetic acid + O 3 (reaction (1b)) and acetoxy + OH + O 2 (reaction (1c)). A recent experimental study has reported branching fractions for these three pathways ( α 1a , α 1b , and α 1c ) from 229 K to 294 K. We constructed a theoretical model for predicting α 1a , α 1b , and α 1c using quantum chemical and Rice–Ramsperger–Kassel–Marcus/master equation (RRKM/ME) simulations. Our main quantum chemical method was Weizmann-1 Brueckner Doubles (W1BD) theory; we combined W1BD and equation-of-motion spin-flip coupled cluster (SF) theory to treat open-shell singlet structures. Using RRKM/ME simulations that included all conformers of acetylperoxy–HO 2 pre-reactive complexes led to a 298 K triplet rate constant, k 1a = 5.11 × 10 −12 cm 3 per molecule per s, and values of α 1a in excellent agreement with experiment. Increasing the energies of all singlet structures by 0.9 kcal mol −1 led to a combined singlet rate constant, k 1b+1c = 1.20 × 10 −11 cm 3 per molecule per s, in good agreement with experiment. However, our predicted variations in α 1b and α 1c with temperature are not nearly as large as those measured, perhaps due to the inadequacy of SF theory in treating the transition structures controlling acetic acid + O 3 formation vs. acetoxy + OH + O 2 formation. 

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4. Sensitized Photooxidation of Ortho ‐Prenyl Phenol: Biomimetic Dihydrobenzofuran Synthesis and Total ¹O₂ Quenching ^†

   https://doi.org/10.1111/php.13689  

   Jabeen, Shakeela; Ghosh, Goutam; Lapoot, Lloyd; Durantini, Andrés M.; Greer, Alexander (September 2022, Photochemistry and Photobiology)

   Abstract The sensitized photooxidation ofortho‐prenyl phenol is described with evidence that solvent aproticity favors the formation of a dihydrobenzofuran [2‐(prop‐1‐en‐2‐yl)‐2,3‐dihydrobenzofuran], a moiety commonly found in natural products. Benzene solvent increased the total quenching rate constant (k_T) of singlet oxygen with prenyl phenol by ~10‐fold compared to methanol. A mechanism is proposed with preferential addition of singlet oxygen to prenyl site due to hydrogen bonding with the phenol OH group, which causes a divergence away from the singlet oxygen ‘ene’ reaction toward the dihydrobenzofuran as the major product. The reaction is a mixed photooxidized system since an epoxide arises by a type I sensitized photooxidation. 

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5. Chiral π-Conjugated Double Helical Aminyl Diradical with the Triplet Ground State

   https://doi.org/10.1055/a-2379-9406  

   Guo, Haoxin; Rajca, Andrzej (February 2025, Synlett)

   Abstract We describe effective development of the highly diastereoselective synthesis of double helical tetraamine 2-H2-C2 and propose a mechanism for its formation. The resolution of 2-H2-C2 is facilitated by a high racemization barrier of 43 kcal mol–1 and it is implemented via either a chiral auxiliary or preparative supercritical fluid chromatography. This enables preparation of the first high-spin neutral diradical, with spin density delocalized within an enantiomeric double helical π-system. The presence of two effective 3-electron C–N bonds in the diradical leads to: (1) the triplet (S = 1) high-spin ground state with a singlet-triplet energy gap of 0.4 kcal mol–1 and (2) the long half-life of up to 6 days in 2-MeTHF at room temperature. The diradical possesses a racemization barrier of at least 26 kcal mol–1 in 2-MeTHF at 293 K and chiroptical properties, with an absorption anisotropy factor |g| ≈ 0.005 at 548 nm. These unique magnetic and optical properties of our diradical form the basis for the development of next-generation spintronic devices. 1 Introduction 2 Synthesis and Resolution of the C 2-Symmetric Double Helical Tetraamine 2-H2-C 2 3 Synthesis and Characterization of Neutral High-Spin Aminyl Diradical 22• -C 2 4 Conclusion 

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