The in situ metalation of monolayers and multilayers of 2H-tetraphenylporphyrin (2HTPP) with Fe atoms on Ag(111) was studied with scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). This surface-confined coordination reaction results in the formation of adsorbed iron(II)-tetraphenylporphyrin (FeTPP). It is demonstrated that metalation of 2HTPP is achieved either by depositing iron atoms onto a monolayer of 2HTPP at room temperature or, alternatively, by depositing 2HTPP onto a Ag(111) surface with predeposited iron. The latter route requires elevated temperatures, indicating that this reaction includes at least one step with an activation barrier. In addition, it is demonstrated that vapor deposited Fe atoms also react with multilayers of the porphyrin at room temperature under the formation of FeTPP.

A systematic scanning tunnelling microscopy study of the self-assembly, intramolecular conformation and supramolecular ordering of different tetraphenylporphyrins (xTPP) with or without a central metal atom (x = 2H, Fe, Co) on Ag(111) at room temperature is presented. The investigation covers a wide range, i.e. the adsorption behaviour from the low sub-monolayer up to the multilayer regime is described in detail and conclusively discussed in regard to molecule-molecule and molecule-substrate interactions. At monolayer coverage the molecules self-assemble in domains with a square unit cell caused by "T-type" intermolecular interactions, while the orientation of the domains along the symmetry axes is determined by adsorbate-substrate interactions. Interestingly for ordered monolayers domain boundaries always separate domains of different organizational chirality but same orientation of the square unit cell. This demonstrates that in the particular system chirality obviously restricts the long range order of the supramolecular TPP assemblies. In combination with DFT calculations it is also demonstrated that the previously reported intramolecular saddle shape deformation of TPPs upon adsorption is more pronounced for metallo-TPP than for 2HTPP.

An ordered monolayer of phthalocyanine on a silver(111) surface reacts with the stoichiometric amount of coadsorbed Fe atoms to form iron(II)-phthalocyanine. This surface-confined redox reaction was studied with X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). The formation of iron(II)-phthalocyanine was confirmed by comparison with the directly deposited complex. No side reactions such as the coordination of Fe atoms on the peripheral nitrogen atoms of the phthalocyanine molecules were observed.

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We study the modification of the growth behaviour of iron on Ag(111) by preadsorbed monolayers of 2H-phthalocyanine (2HPc) and 2H-tetraphenylporphyrin (2HTPP) by scanning tunneling microscopy, upon Fe deposition in ultra-high vacuum at room temperature. The growth of iron on clean Ag(111) follows the scheme expected from reports of similar systems: For low coverages (up to~0.3 ML) an almost exclusive agglomeration of iron clusters at step edges occurs, which continue to grow in a dendritic fashion at higher coverages. Upon deposition onto Ag(111) precovered with monolayers of 2HTPP and 2HPc, at coverages up to 0.037 ML no growth of Fe islands but complete metalation, i.e., incorporation of the Fe atoms in the macrocyle of the preadsorbed molecules is found. For higher amounts of deposited Fe (0.037 < θ Fe < 0.30 ML), the formation of Fe islands is observed, which occurs differently for 2HPC and 2HTPP. While on 2HTPP two-dimensional islands are formed presumably underneath a FeTPP monolayer, for 2HPc the Fe growth is dominated by the formation of small 3D clusters within a FePc monolayer. At θ Fe = 2.0 ML, both systems exhibit small three dimensional Fe islands. These results are discussed considering different aspects like the molecular conformation of FeTPP and FePc on Ag(111) and the diffusional properties of Fe on the clean and modified substrate.