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Controlling the Dimensionality of On-Surface Coordination Polymers via Endo- or Exoligation
The
formation of on-surface coordination polymers is controlled
by the interplay of chemical reactivity and structure of the building
blocks, as well as by the orientating role of the substrate registry.
Beyond the predetermined patterns of structural assembly, the chemical
reactivity of the reactants involved may provide alternative pathways
in their aggregation. Organic molecules, which are transformed in
a surface reaction, may be subsequently trapped via coordination of
homo- or heteroÂmetal adatoms, which may also play a role in
the molecular transformation. The amino-functionalized perylene derivative,
4,9-diaminoÂperylene quinone-3,10-diimine (DPDI), undergoes specific
levels of dehydrogenation (−1 H<sub>2</sub> or −3 H<sub>2</sub>) depending on the nature of the present adatoms (Fe, Co,
Ni or Cu). In this way, the molecule is converted to an endo- or an
exoligand, possessing a concave or convex arrangement of ligating
atoms, which is decisive for the formation of either 1D or 2D coordination
polymers