Radiolysis and photolysis of crystalline 2,4,6-triazido-3,5-dichloropyridine: Generation of Quintet dinitrenes |
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Authors: | S I Kuzina A I Mikhailov S V Chapyshev |
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Institution: | (1) Institute of Problems of Chemical Physics, Russian Academy of Sciences, pr. Akademika Semenova 1, Chernogolovka, Moscow oblast, 142432, Russia |
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Abstract: | Low-temperature radiolysis and photolysis of crystalline 2,4,6-triazido-3,5-dichloropyridine (TAP) were studied by means of the ESR technique. It was found that the long-term irradiation of TAP at 77 K leads to the appearance of characteristic signals of quintet 2,6-dinitreno-4-azido-3,5-dichloropyridine and 2,4-dinitreno-6-azido-3,5-dichloropyridine; their radiation-chemical yield was 0.035 and 0.012 molecule/100 eV, respectively. The photolysis of crystalline 2,4,6-triazido-3,5-dichloropyridine proceeded less effectively, producing only quintet 2,6 dinitrene with a quantum yield of ~4.5 × 10?4. The study showed that the generation of high-spin nitrenes via radiolysis of crystalline azides is much superior to the photochemical technique in efficiency and may be of practical importance for the preparation of magnetically active organic materials. |
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