The organization and thermal lability of chloro(5,10,15,20-tetraphenyl porphyrinato)manganese(III) (Cl-MnTPP) molecules on the Ag(111) surface have been investigated under ultra-high vacuum conditions, using scanning tunnelling microscopy, low energy electron diffraction and x-ray photoelectron spectroscopy. The findings reveal the epitaxial nature of the molecule-substrate interface, and moreover, offer a valuable insight into the latent coordination properties of surface-confined metalloporphyrins. The Cl-MnTPP molecules are found to self-assemble on the Ag(111) surface at room temperature, forming an ordered molecular overlayer described by a square unit cell. In accordance with the threefold symmetry of the Ag(111) surface, three rotationally equivalent domains of the molecular overlayer are observed. The primitive lattice vectors of the Cl-MnTPP overlayer show an azimuthal rotation of ±15° relative to those of the Ag(111) surface, while the principal molecular axes of the individual molecules are found to be aligned with the substrate (0(-)11) and ((-)211) crystallographic directions. The axial chloride (Cl) ligand is found to be orientated away from the Ag(111) surface, whereby the average plane of the porphyrin macrocycle lies parallel to that of the substrate. When adsorbed on the Ag(111) surface, the Cl-MnTPP molecules display a latent thermal lability resulting in the dissociation of the axial Cl ligand at ~423 K. The thermally induced dissociation of the Cl ligand leaves the porphyrin complex otherwise intact, giving rise to the coordinatively unsaturated Mn(III) derivative. Consistent with the surface conformation of the Cl-MnTPP precursor, the resulting (5,10,15,20-tetraphenyl porphyrinato)manganese(III) (MnTPP) molecules display the same lattice structure and registry with the Ag(111) surface.

The room temperature growth and ordering of (porphyrinato)nickel (II) (or nickel (II) porphine, NiP) molecules on a Ag(111) surface have been investigated using scanning tunnelling microscopy and low-energy electron diffraction (LEED). At a coverage of one monolayer, NiP molecules form a well-ordered molecular layer, having a hexagonal structure, on the Ag(111) surface. Porphyrin molecules have a flat orientation in this overlayer with the molecular plane lying parallel to the substrate. LEED data obtained from one monolayer of the NiP on the Ag(111) surface show the formation of two mirror domains each rotated either clockwise or anticlockwise by 6 degrees with respect to the substrate. NiP molecules forming a second layer self-assemble into well-ordered and uniformly separated nanolines at room temperature. These nanolines consist of hexagonally ordered NiP molecules and are found to be 1-4 molecules wide, depending on the molecular coverage. The completed second monolayer preserves the same planarity and hexagonal ordering as the first molecular layer but with a 4% lateral relaxation which produces a periodic modulation of approximately 5 nm.

The room-temperature growth and ordering of (porphyrinato)nickel(II) (nickel(II) porphine, NiP) molecules on the Ag/Si(111)-( √ 3 × √ 3)R30 • surface have been investigated using scanning tunnelling microscopy/spectroscopy (STM/STS) and low-energy electron diffraction (LEED). The results indicate a well-ordered molecular layer in which the porphyrin molecules have a flat orientation with the molecular plane lying parallel to the substrate and forming a hexagonal overlayer on the surface. STM and LEED data obtained from one monolayer (ML) of the NiP on the Ag/Si(111)-( √ 3 × √ 3)R30 • surface show the formation of two well-ordered mirror domains, each rotated either clockwise or counterclockwise by 7 • with respect to the substrate. A hexagonal Moiré pattern was observed for the NiP overlayer due to long-range variation in the overlayer-substrate distance. It was found that the existence of such azimuthal rotation and the Moiré pattern are caused by a lattice mismatch between the substrate and the molecular overlayer, and a corresponding model is proposed. The NiP molecules forming the second monolayer maintain the same planarity and hexagonal ordering as the first molecular layer. Scanning tunnelling spectroscopy data obtained from the NiP overlayer on the Ag/Si(111)-( √ 3 × √ 3)R30 • surface show good agreement with density functional theory calculations.

The covalent coupling of (5,10,15,20-tetrabromothien-2-ylporphyrinato)zinc(II) (TBrThP) molecules on the Ag(111) surface has been investigated under ultra-high-vacuum conditions, using scanning tunnelling microscopy and x-ray photoelectron spectroscopy. The findings provide atomic-level insight into surface-confined Ullmann coupling of thiophene substituted porphyrins, analyzing the progression of organometallic intermediate to final coupled state. Adsorption of the TBrThP molecules on the Ag(111) surface at room temperature is found to result in the reductive dehalogenation of the bromothienyl substituents and the subsequent formation of single strand and crosslinked coordination networks. The coordinated substrate atoms bridge the proximal thienyl groups of the organometallic intermediate, while the cleaved bromine atoms are bound on the adjacent Ag(111) surface. The intermediate complex displays a thermal lability at ∼423 K that results in the dissociation of the proximal thienyl groups with the concomitant loss of the surface bound bromine. At the thermally induced dissociation of the intermediate complex the resultant thienylporphyrin derivatives covalently couple, leading to the formation of a polymeric network of thiophene linked and meso-meso fused porphyrins.

The room temperature self-assembly and ordering of (5,15-diphenylporphyrinato)nickel(II) (NiDPP) on the Ag(111) and Ag/Si(111)-(√3 × √3)R30º surfaces have been investigated using scanning tunnelling microscopy and low-energy electron diffraction. The self-assembled structures and lattice parameters of the NiDPP monolayer are shown to be extremely dependent on the reactivity of the substrate, and probable molecular binding sites are proposed. The NiDPP overlayer on Ag(111) grows from the substrate step edges, which results in a single-domain structure. This close-packed structure has an oblique unit cell and consists of molecular rows. The molecules in adjacent rows are rotated by approximately 17° with respect to each other. In turn, the NiDPP molecules form three equivalent domains on the Ag/Si(111)-(√3 × √3)R30º surface, which follow the three-fold symmetry of the substrate. The molecules adopt one of three equivalent orientations on the surface, acting as nucleation sites for these domains, due to the stronger molecule-substrate interaction compared to the case of the Ag(111). The results are explained in terms of the substrate reactivity and the lattice mismatch between the substrate and the molecular overlayer.