Reflection-absorption infrared spectroscopy (RAIRS) has been used to study
in detail, as a function of temperature and coverage, the interaction of py
romellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) on the clean and o
xygen-precovered Cu{110} surfaces. On the clean surface, both molecules sho
w coverage-dependent reorientation from flat lying to upright species. The
adsorption of PMDA on the clean surface leads to a ring-opening reaction of
one of the anhydride group to produce a. species with both carbonyl and ca
rboxylate groups. The carbonyl group is lost into the gas phase above 350 K
. with the resulting anhydride species bonded to the surface via the carbox
ylate group. The presence of preadsorbed oxygen also leads to the reaction
of one of the anhydride soups, although in this case a dicarboxylate (phtha
late) anhydride species is produced. The condensation reaction of 4,4-oxydi
aniline with the two PMDA-derived species has also been studied. It is show
n that the PMDA-ODA oligomer can be grown layer by layer using controlled i
mide coupling reactions. The growth is monitored by IR spectroscopy.