ISOMERIZATION AND DECOMPOSITION OF A POLY(ALKYLARYLDIAZOSULFIDE) - COMPARISON OF THERMOLYTICALLY AND PHOTOLYTICALLY INDUCED REACTIONS

The poly(alkylaryldiazosulfide) compound I has been synthesized to yie ld preferably the thermodynamically instable Z-isomer, in a mixture of E- and Z-isomers with respect to the N=N bond. Thermolytically and ph otolytically induced isomerization as well as decomposition of I are m onitored 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 a t 308 nm. UV/Vis absorption spectra indicate a preferred consumption o f the E-isomer. There is evidence for a photochemical decomposition in cluding a rearrangement of the E-isomer into the Z-form as an intermed iate reaction step.