The fabrication of large molecular devices, directly on surfaces in UHV conditions, by covalent coupling of smaller precursors has become in the past years an attractive solution for Molecular Electronics. This review presents the state-of-the-art and an analysis of the potential of this new field, from Ullmann type C–C coupling, cyclodehydrogenation, and reactions involving heteroelements to 2D polymerisation on insulating thin films. Mechanistic insights are also mentioned, giving preliminary explanations on the influence of the substrate and the 2D confinement. Potential perspectives for further developments are then evoked.
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