| Abstract: | The poly(alkylaryldiazosulfide) compound I has been synthesized to yield preferably the thermodynamically instable Z-isomer, in a mixture of E- and Z-isomers with respect to the N=N bond. Thermolytically and photolytically induced isomerization as well as decomposition of I are monitored by means of infrared and UV/Vis absorption spectroscopy. The activation energy of the Z/E-isomerization is determined to be around 103 kJ mol–1, independent of the matrix used. The activation energy of the thermolytically induced release of nitrogen is 153 kJ mol–1. The photolytic decomposition of I is induced by excimer laser pulses at 308 nm. UV/Vis absorption spectra indicate a preferred consumption of the E-isomer. There is evidence for a photochemical decomposition including a rearrangement of the E-isomer into the Z-form as an intermediate reaction step. |
