Chemiluminescence during thermolysis of the (Ph3COOCPh3)n—Ph3C· peroxide containing captured triphenylmethyl radical

Chemiluminescence (CL) in the thermolysis of (Ph3COOCPh3)n—Ph3C· containing the triphenylmethyl radical captured during the synthesis of Gomberg's peroxide was found. Two CL emitters were identified: the triplet state of benzophenone (3Ph2CO*) and Ph3C·*. Ph3C·* is formed due to the energy transfer from the excited 3Ph2CO* generated in the disproportion of thermolysis intermediates, Ph3CO· radicals. This Ph3C·* luminescence is the first example of CL activation by an organic radical. Chemiluminescence during the thermolysis of Ph3COOCPh3 containing no Ph3C· is resulted from the emission of one emitter, 3Ph2CO*. The solid-phase CL was found during the oxidation of Ph3C· with dioxygen after the destruction of the crystalline lattice as a result of the thermolysis of the (Ph3COOCPh3)n—Ph3C· peroxide.