Role of the Anchored Groups in the Bonding and Self-Organization
of Macrocycles: Carboxylic versus Pyrrole Groups
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Abstract
A combination of variable temperature
scanning tunneling microscopy,
near edge X-ray adsorption fine structure and density functional theory
has been used to investigate the chemisorption and self-assembly of
metal-free protoporphyrin IX molecules on Cu(110) surface. The molecules
in contact with the substrate suffer irreversible molecular transformations,
mainly deprotonation of the carboxylic groups and metalation of the
pyrroline subunits. The carboxylate group has been revealed as the
anchored group versus the tetrapyrrole ring. We study the role played
by the carboxylic acid groups in the surface-molecular bonding and
how its presence affects the supramolecular structure