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The reactions of 3,4,9,10-perylenetetracarboxylic dianhydride with 4,4′-diamino-p-terphenyl and with 2,4,6-tris(4-aminophenyl)-1,3,5-triazine on an Au(111) surface have been followed by low-temperature UHV-STM in the range of 300 to 700 K at coverages of up to one monolayer. Well-ordered, H-bonded structures are observed even after annealing at temperatures up to 470 K, while above 550 K reaction is initiated with evidence of amic acid intermediates. At higher temperatures, full imidisation leads to a covalently linked, surface polyimide networks. There is evidence of gold reconstruction playing a role in the early stages of imidisation and signs of limited order in the final polyimide. With the diamine as precursor, 1D-interconnectivity results, while with the triamine as partner, full 2D-connectivity is possible. In contrast to the situation in the bulk, the intermediate amic acid seems to be less stable and iso-imides are common in the final networks, as witnessed by the conformation of the product and the prevalence of triangular features in the case of the polyimide formed from the triamine precursor.
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Physical Chemistry Chemical Physics
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