Direct photochemical excitation of the polycyclic azoalkane 1 yields a mixture of (CH)6 isomers as major products at room temperature and the 1,2‐diaza‐cyclooctatetraene 2 as the major product at − 78°C. The ratio of (CH)6 isomers to 2 is strongly dependent on solvent. For example, at room temperature the ratio (CH)6/2 is 92/8 in pentane and 38/62 in dimethyl sulfoxide. Triplet photosensitized excitation of 1 yields 2 as the major product. The triplet reaction is insensitive to temperature and solvent. These results are consistent with reaction of S1(1) to yield predominately (CH)6 isomers via a thermally activated nitrogen extrusion, whereas T1(1) yields predominantly 2 via a temperature and solvent independent rearrangement. Quantitative measurement of photochemical and photoluminescence parameters reveals that the solvent effect on the product distribution in the direct photolysis of 1 is due to a combination of the influence of solvent on the rate of reaction from S1 and the rate of intersystem crossing from S1.
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