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Solid-state photoreactions are generally controlled by the rigid and ordered nature of crystals. Herein, the solution and solid-state photoreactivities of carbonylbis(4,1-phenylene)dicarbonazidate (1) were investigated to elucidate the solid-state reaction mechanism. Irradiation of 1 in methanol yielded primarily the corresponding amine, whereas irradiation in the solid state gave a mixture of photoproducts. Laser flash photolysis in methanol showed the formation of the triplet ketone (TK) of 1 (τ ∼ 99 ns), which decayed to triplet nitrene 31N (τ ∼ 464 ns), as assigned by comparison to its calculated spectrum. Laser flash photolysis of a nanocrystalline suspension and diffuse reflectance laser flash photolysis also revealed the formation of TK of 1 (τ ∼ 106 ns) and 31N (τ ∼ 806 ns). Electron spin resonance spectroscopy and phosphorescence measurements further verified the formation of 31N and the TK of 1, respectively. In methanol, 31N decays by H atom abstraction. However, in the solid state, 31N is sufficiently long lived to thermally populate its singlet configuration (11N). Insertion of 11N into the phenyl ring to produce oxazolone competes with 31N cleavage to form a radical pair. Notably, 1 did not exhibit photodynamic behavior, likely because the photoreaction occurs only on the crystal surfaces.more » « lessFree, publicly-accessible full text available November 8, 2024
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Free, publicly-accessible full text available June 16, 2024
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ABSTRACT Triplet arylnitrenes may provide direct access to aryl azo‐dimers, which have broad commercial applicability. Herein, the photolysis of
p ‐azidostilbene (1 ) in argon‐saturated methanol yielded stilbene azo‐dimer (2 ) through the dimerization of tripletp ‐nitrenostilbene (31N ). The formation of31N was verified by electron paramagnetic resonance spectroscopy and absorption spectroscopy (λ max ~ 375 nm) in cryogenic 2‐methyltetrahydrofuran matrices. At ambient temperature, laser flash photolysis of1 in methanol formed31N (λ max ~ 370 nm, 2.85 × 107 s−1). On shorter timescales, a transient absorption (λ max ~ 390 nm) that decayed with a similar rate constant (3.11 × 107 s−1) was assigned to a triplet excited state (T) of1 . Density functional theory calculations yielded three configurations for T of1 , with the unpaired electrons on the azido (TA) or stilbene moiety (TTw, twisted and TFl, flat). The transient was assigned to TTwbased on its calculated spectrum. CASPT2 calculations gave a singlet–triplet energy gap of 16.6 kcal mol−1for1 N ; thus, intersystem crossing of11N to31N is unlikely at ambient temperature, supporting the formation of31N from T of1 . Thus, sustainable synthetic methods for aryl azo‐dimers can be developed using the visible‐light irradiation of aryl azides to form triplet arylnitrenes.