Ultraviolet photoelectron spectroscopy study of the thermochromic phase transition in urethane-substituted polydiacetylenes.

Threshold solid-state ionization energies determined from ultraviolet photoelectron spectra are reported for the thermochromic polydiacetylenes (PDAs) from the bis-ethyl- and bis-n-propyl urethanes of 5,7-dodecadiyn-1,12-diol (ETCD and PUDO, respectively) and the nonthermochromic 1,6-bis-p-toluenesulfonate of 2,4-hexadiyne-1,6-diol (PTS) at temperatures above and below the thermochromic phase transition. PDA-PTS has an ionization energy of 5.66 eV which does not change significantly as the temperature is raised above 140 degrees C. At 25 degrees C, PDA-ETCD and PDA-PUDO have threshold ionization energies of 5.65 and 5.51 eV, respectively. The ionization energies of these PDAs increase by approximately 0.34 eV as temperature is raised above 140 degrees C and returns to the lower values as temperature is reduced to 25 degrees C. The magnitude of the increase in ionization energy on heating to temperatures above the thermochromic transition is very close to the shift in energy of the electronic spectrum over the same temperature range. These observations suggest that the structural changes that take place in the course of the thermochromic transition are primarily associated with the valence band and are consistent with partial relief of mechanical strains.