Comparing Cyanophenyl and Pyridyl Ligands in the Formation of Porphyrin-Based Metal-Organic Coordination Networks.

In recent studies, porphyrin derivatives have been frequently used as building blocks for the fabrication of metal-organic coordination networks (MOCNs) on metal surfaces under ultrahigh vacuum conditions (UHV). The porphyrin core can host a variety of 3d transition metals, which are usually incorporated in solution. However, the replacement of a pre-existing metal atom in the porphyrin core by a different metallic species has been rarely reported under UHV. Herein, we studied the influence of cyanophenyl and pyridyl functional endgroups in the self-assembly of structurally different porphyrin-based MOCNs by the deposition of Fe atoms on tetracyanophenyl (Co-TCNPP) and tetrapyridyl-functionalized (Zn-TPPyP) porphyrins on Au(111) by means of scanning tunneling microscopy (STM). A comparative analysis of the influence of the cyano and pyridyl endgroups on the formation of different in-plane coordination motifs is performed. Each porphyrin derivative formed two structurally different Fe-coordinated MOCNs stabilized by three- and fourfold in-plane coordination nodes, respectively. Interestingly, the codeposited Fe atoms did not only bind to the functional endgroups but also reacted with the porphyrin core of the Zn-substituted porphyrin (Zn-TPyP), i.e., an atom exchange reaction took place in the porphyrin core where the codeposited Fe atoms replaced the Zn atoms. This was evidenced by the appearance of molecules with an enhanced (centered) STM contrast compared with the appearance of Zn-TPyP, which suggested the formation of a new molecular species, i.e., Fe-TPPyP. Furthermore, the porphyrin core of the Co-substituted porphyrin (Co-TCNPP) displayed an off-centered STM contrast after the deposition of Fe atoms, which was attributed to the binding of the Fe atoms on the top site of the Co-substituted porphyrin core. In summary, the deposition of metal atoms onto organic layers can steer the formation of structurally different MOCNs and may replace pre-existing metal atoms contained in the porphyrin core.

Structural Transformation of Surface-Confined Porphyrin Networks by Addition of Co Atoms.

The self-assembly of a nickel-porphyrin derivative (Ni-DPPyP) containing two pyridyl coordinating sites and two pentyl chains at trans meso positions was studied with scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) on Au(111). Deposition of Ni-DPPyP onto Au(111) gave rise to a close-packed network for coverages smaller or equal to one monolayer as revealed by STM and LEED. The molecular arrangement of this two-dimensional network is stabilized via hydrogen bonds formed between the pyridyl's nitrogen and hydrogen atoms from the pyrrole groups of neighboring molecules. Subsequent deposition of cobalt atoms onto the close-packed network and post-deposition annealing at 423 K led to the formation of a Co-coordinated hexagonal porous network. As confirmed by XPS measurements, the porous network is stabilized by metal-ligand interactions between one cobalt atom and three pyridyl ligands, each pyridyl ligand coming from a different Ni-DPPyP molecule.

Coverage-Dependent Structural Transformation of Cyano-Functionalized Porphyrin Networks on Au(111) via Addition of Cobalt Atoms.

The self-assembly process of a cobalt-porphyrin derivative (Co-TCNPP) containing cyanophenyl substituents at all four meso positions on Au(111) was studied by means of scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) under ultrahigh vacuum conditions. Deposition of Co-TCNPP onto Au(111) gave rise to the formation of a close-packed H-bonded network, which was independent of coverage as revealed by STM and LEED. However, a coverage-dependent structural transformation took place upon the deposition of Co atoms. At monolayer coverage, a reticulated long-range ordered network exhibiting a distinct fourfold Co coordination was observed. By reduction of the molecular coverage, a second metal-organic coordination network (MOCN) was formed in coexistence with the fourfold Co-coordinated network, that is, a chevron structure stabilized by a simultaneous expression of H-bonding and threefold Co coordination. We attribute the coverage-dependent structural transformation to the in-plane compression pressure exerted by the molecules deposited on the surface. Our study shows that a subtle interplay between the chemical nature of the building blocks (molecules and metallic atoms) and molecular coverage can steer the formation of structurally different porphyrin-based MOCNs.