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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. 

Sunlight‐driven photochemical reactions are an important tool for sustainable organic synthesis. However, compared with ground states, for which the effects of structure on properties and reactivity are well established, the understanding of excited states is limited. In particular, an improved understanding of aromaticity and antiaromaticity in excited states is necessary to develop strategic photochemical methods for synthesizing polycyclic aromatic compounds. Herein, using density functional theory (DFT)‐optimized structures, the ground singlet (S₀) and lowest triplet (T₁) states of coronene and corannulene were compared. Bond length analysis demonstrated that both triplet corannulene and triplet coronene bear a partial resemblance to benzene. Nucleus‐independent chemical shift (NICS(0), NICS(1.7)_ZZ, NICS scans) and anisotropy of the induced current density (ACID) calculations were carried out to compare the induced magnetic currents in these molecules. This analysis demonstrated rather weak π‐conjugation and partial antiaromaticity in the S₀state of each molecule. In contrast, a combination of circular induced currents and pronounced antiaromaticity was found in the T₁state of each molecule. However, the T₁of corannulene exhibited higher stability, which should facilitate functionalization. Consequently, corannulene is considered more suitable for photochemical applications.

 

To enhance the versatility of organic azides in organic synthesis, a better understanding of their photochemistry is required. Herein, the photoreactivity of azidoisoxazole 1 was characterized in cryogenic matrices with IR and UV-Vis absorption spectroscopy. The irradiation (λ = 254 nm) of azidoisoxazole 1 in an argon matrix at 13 K and in glassy 2-methyltetrahydrofuran (mTHF) at 77 K yielded nitrosoalkene 3. Density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations were used to aid the characterization of nitrosoalkene 3 and to support the proposed mechanism for its formation. It is likely that nitrosoalkene 3 is formed from the singlet excited state of azidoisoxazole 1 via a concerted mechanism or from cleavage of an intermediate singlet nitrene that does not undergo efficient intersystem crossing to its triplet configuration.