Fundamental understanding of the bonding motifs that elaborately mediate the formation of supramolecular nanostructures is essential for the rational design of stable artificial organic architectures. Herein, the structural transformation of the adsorption complex of 2, 7-dibromopyrene (Br2 Py) on the Au(111) surface has been investigated by scanning tunnelling microscopy combined with X-ray photoemission spectroscopy and density function theory calculations. In the initial stage of self-assembly, well ordered patterns are formed in the manner of extended supramolecular structures balanced by intermolecular halogen bonding motifs, whilst the Au(111) reconstruction is still fairly visible. Subsequent thermal annealing promotes the dehalogenation and on-surface Ullmann coupling, and polymerized oligomers are consequently constructed. Interestingly, such polymerized chains are still stably mediated by the halogen bonding motif via dissociated Br atoms which are revealed to be absorbed on the bridge site of Au(111), while the number of halogen bonds increases significantly from self-assembly to Ullmann coupling polymerization, indicating that the halogen bonding motif contributes significantly to the extended one-dimensional polymers.
Keywords: STM; Ullmann coupling; gold; halogen bonding; self-assembly.
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