SPM tools have been extensively used in recent years to prepare, characterize and test the structural and functional properties of self-assembled molecular networks on surfaces. In many cases the molecular positional and conformational degrees of freedom determine a complex interfacial energy landscape, where subtle equilibria lead to the formation of various 2D ordered phases, often related to each other by phase transitions able to trigger the molecular reactivity, which therefore depends on subtle interrelations between local adsorption sites, intramolecular structure and long range supramolecular order. This talk will address some aspects of the structure-reactivity relationships in several surface-supported molecular networks, studied by means of STM complemented by other surface science and computational tools: e.g. the dependence of the catalytic activity toward oxygen reduction and of the magnetic properties of an Ag-supported iron phthalocyanine monolayer on the supramolecular arrangement of the molecules [1]; the requirements for either thermal [2] or photo-excited [3] covalent stabilization of single- and bicomponent supramolecular networks containing functionalized porphyrins on Ag low-index surfaces; the bottom up synthesis of long range ordered 1D poly-para-phenylene nanowires and 2D graphene nanoribbons on gold substrates [4]. [1] Casarin et al., J. Phys. Chem. C, 2010 ,114, 2144; Sedona, F. et al. Nat. Mater, 2012, 11, 970, Bartolom\ue9 et al. J. Phys. Chem. C, 2015 ,119, 12488. [2] Di Marino et al., Langmuir, 2010, 26, 2466; Sedona et al., ACS Nano, 2010, 4, 5147; Sedona et al. J. Phys. Chem. C, 2014 ,118, 1587. [3] Basagni et al., Chem. Eur. J. 2014, 20, 14296. [4] Basagni et al., J. Am. Chem. Soc. 2015, 137, 1802; Basagni et al., ACS Nano 2016, 10, 2644
