The thesis at hand addresses the adsorption behavior of different tetraphenylporphyrin derivatives (naphthyl and cyano functionalization) on single crystal surfaces at and around RT by scanning tunneling microscopy. It presents a detailed investigation and discussion of intramolecular conformation, diffusion behavior, role of intermolecular interactions in the formation of supramolecular structures, and the interaction and reaction with coadsorbed metal atoms, which sets the stage for the fabrication of functional nanostructures from porphyrins. The publications [P2 and P4] address the adsorption behavior of the naphthyl-functionalized porphyrins 2HTNP and 2HTNBP. We observe a very peculiar adsorption behavior of 2HTNP molecules on Cu(111): Individual molecules are found to adsorb in the “inverted” conformation with upright standing pyrrole rings at RT, which are orientated along the main crystallographic directions of the substrate. Due to the asymmetry of the naphthyl groups, 16 different surface conformers are possible, 10 of which have a different appearance and could indeed be identified by STM. Interestingly, 2HTNBP molecules adsorb as individual molecules as well. On Cu(111), no island formation of 2HTNBP occurs, which indicates a strong interaction of this porphyrin with the substrate, similar to 2HTPP and 2HTNP. The possible driving forces could be a coordination of the iminic nitrogen atoms of the isoindole groups to Cu substrate atoms, like for 2HTPP and 2HTNP, and the larger footprint of the molecules. The investigation of the diffusion behavior of both molecules shows different mobilities, which can be classified into three categories, that is, low, medium, and high. While for 2HTNBP no information of the naphthyl orientation could be linked to the different mobilities, the mobility of 2HTNP is related to the naphthyl orientation relative to the main axis of the molecule along the iminic nitrogen atoms. Fast diffusing species have 3 or 4 naphthyl groups in τ-orientation (pointing in the direction of the movement, which is aligned with the crystallographic axis). Immobile species have only 0 or 1 naphthyl groups orientated in this direction, which equals 4 or 3 groups in α- orientation (away from the main molecular axis and diffusion direction). This behavior shows that the introduction of asymmetric functional groups in the periphery linked to the macrocycle via single C−C bonds can have a strong influence on the adsorption behavior by yielding a variety of non-chiral and chiral conformers, which behave differently in their diffusion. To expand our understanding of the influence of the asymmetric naphthyl group on the adsorption behavior of 2HTNP and 2HTNBP, we studied the adsorption behavior on Ag(111)as well. For 2HTNP on Ag(111), we observed a commensurable 7 -2 / 0 5 structure, leading to identical adsorption sites for each molecule on the surface. Upon annealing to 600 K, the commensurability with the substrate is lost and the structure transforms into a denser packed arrangement. Notably, the distance along one unit cell vector remains unchanged; however, it is no longer aligned along one of the surface high symmetry axes, resulting in only every third molecule sitting on the same adsorption site on the surface (within the margin of error). For 2HTNBP, we observed also island formation on Ag(111) at RT in non-commensurable structures, which are stabilized by T-type interactions between the naphthyl-groups of neighboring molecules. Upon annealing to 500 K, the structure converts to a structure with a slightly higher density, which is now stabilized by π-π stacking of neighboring naphthyl groups. Our studies reveal a pronounced difference of the adsorption of the porphyrins on Cu(111) and Ag(111) surfaces, which is maintained when the pyrrole groups are replaced by an isoindole group and the phenyl groups by naphthyl groups. In summary, the flexibility of the naphthyl group allows for the formation of different conformers on the reactive Cu(111), and structural motifs based on repulsive interactions occurring at too close specific adsorption sites or attractive interactions via T-type bonding or π-π stacking arrangements on Ag(111). The second part of this thesis focusses on the interaction and reaction of cyanofunctionalized phenylporphyrins 2HtransDCNPP and 2HTCNPP with metal atoms (Co and Zn) and is based on the publications [P1 and P3]. On Ag(111), 2HtransDCNPP molecules exhibit a bifunctional behavior toward coadsorbed Co atoms. In a first step, the four N atoms in the macrocycle of the molecules react with Co atoms under the formation of CotransDCNPP (metalation reaction). Cobalt-deposition onto 2HtransDCNPPs leads to a rapid and effective metalation reaction at RT. When switching the deposition order, the metalation reaction requires elevated temperatures. As a second step, the peripheral cyano groups can also coordinate with Co atoms. While a 4-fold coordination motif is preferred, also 3-fold, five-fold and six-fold motifs are observable. The metal–organic coordination structures appear at RT, and annealing at 400 K enhances the coordination process. The metalation reaction of 2HTCNPP with post-deposited Zn atoms to ZnTCNPP on a Ag(111) surface was investigated, and a reaction intermediate (SAT complex) was identified by scanning tunneling microscopy at RT. After Zn deposition onto a 2HTCNPP layer at RT, the formation of three different 2D ordered island types, which coexist on the surface, wasobserved. Within all three island types, a new species could be identified as a bright protrusion, the amount of which correlates with the amount of post-deposited Zn. This species is attributed to a metastable SAT complex. In this SAT complex, the Zn atom coordinates with the macrocycle while the pyrrolic hydrogen atoms are still bound to the nitrogen atoms. This metastable SAT complex has been previously observed by Shubina et al. in the corresponding metalation reaction of the non-cyano-functionalized 2HTPP to ZnTPP, with a characteristic signature in XPS. Upon heating to 500 K, the activation barrier for the subsequent reaction of the intermediate SAT complex to the metalated porphyrin is overcome, yielding ZnTCNPP, and hydrogen desorbs. As an alternative to thermal activation, the barrier for the reaction of the SAT complex to metalated ZnTCNPP can also be overcome by a positive voltage pulse applied to the STM tip. Furthermore, a peculiar long range ordered structure, which covers several terraces of the Ag(111) surface like a carpet, was observed after the deposition of Zn onto a layer of already metalated ZnTCNPP at RT. In conclusion, the thesis at hand gives valuable insights into the adsorption behavior of porphyrins on single crystal metal surfaces like Cu(111) and Ag(111). The functionalization plays a critical role to tailor the peculiar molecular-substrate or molecule-molecule interactions of porphyrins. The presented and discussed results of the publications [P1-4] indicate different strategies to tailor the adsorption behavior of porphyrins on surfaces, and thus deliver a toolbox for the fabrication of functional molecular architectures.