  Molecular functionalization of nanoparticles and metallic substrates can be
used to tune their properties for specific applications. However,
polycrystalline substrates and nanoparticles exhibit surface planes with
distinct crystallographic orientations. Therefore, the development of reliable
strategies for molecular functionalization requires knowledge of the role of
the surface plane orientation in the growth kinetics, structure, and properties
of the molecular layer. Here, we apply a multiscale analysis to investigate the
self-assembly of 4,4'-biphenyl-dicarboxylic acid (BDA) on Ag(111) and
critically discuss the difference to Ag(100). Whereas the structural motifs for
intact and fully deprotonated BDA are similar on both surfaces, the
intermediate phases comprising partially deprotonated BDA differ in the
structure and chemical composition. A real-time view of the phase
transformations enables us to present a generalized picture of the phase
transformations between the self-assembled molecular phases on the surfaces and
underline important features such as the phase stabilization of the chemical
composition and the mechanism of the related burst transformation. The
influence of the substrate orientation on the structure of molecular layers and
phase transformations provides the necessary background for developing
functionalization strategies of the substrates displaying multiple surface
planes and kinetic models for the growth near thermodynamic equilibrium.
