On the adsorption of different tetranaphthylporphyrins on Cu(111) and Ag(111)

Structure and Conformation of Individual Molecules upon Adsorption of a Mixture of Benzoporphyrins on Ag(111), Cu(111), and Cu(110) Surfaces

“…The outer four protrusions, that is, those at the edges of the rectangle always appear dim. By comparison with the chemical structure in Figure 1 and STM reports concerning different porphyrins in literature (see ref [20a,b,25a,27b] . and references therein), we assign them to the peripheral phenyl substituents.…”

“…Benzoporphyrins have a variety of potential practical applications, such as organic near‐infrared devices, [15] oxygen sensors, [16] photodynamic therapy, [17] organic thin‐film transistors, [18] and dye‐sensitized solar cells [14,19] . Despite this relevance, only very few investigations of their adsorption behavior on different metal surfaces have been reported to date: [20] For 2H‐5,10,15,20‐tetrakis‐(2‐naphthyl)‐benzoporphyrin (2H‐TNBP) on Cu(111), individual molecules were observed, whereas islands with square arrangements were observed on Ag(111); [20a] for 2H‐5,10,15,20‐tetrakis(4‐cyanophenyl)‐tetrabenzoporphyrin (2H‐TCNPTBP), Kagome, quadratic lattice, and hexagonal networks coexist on Cu(111); [20b] for 2H‐5,10,15,20‐tetraphenyltetrabenzoporphyrin (2H‐TPTBP), 2D islands with the molecules arranged in a herringbone structure are found on Cu(111) and Ag(111), whereas on Cu(110) 1D molecular chains were observed; [20c] for Ni(II)‐5, 10, 15, 20‐tetraphenyltetrabenzoporphyrin (Ni‐TPBP), oblique, herringbone, and cross structures coexist on Cu(111); [20d] and finally for Ni(II)‐meso‐tetrakis(4‐ tert ‐butylphenyl)‐benzoporphyrin (Ni‐TTBPBP), islands with square arrangement were observed on Cu(111) [20e] . Such arrangements could find potential applications in organic electronics or catalysis.…”

On-Surface Synthesis of Rigid Benzenoid- and Nonbenzenoid-Coupled Porphyrin–Graphene Nanoribbon Hybrids

“…The nc-AFM images (Figure a) reveal two opposing pyrrole groups tilted upward, going in hand with a downward tilting of the naphthalenes, attributed to steric hindrance at the crowded naphthalene–pyrrole positions (gray circles Figure a). Indeed, significant distortions from planarity were reported for closely related β, meso -fused extended porphyrins, based on NMR and X-ray analyses. , Furthermore, such saddle-shaped macrocycle deformations are characteristic of functionalized porphyrins on Au(111) and Ag(111) surfaces. − Though there have been studies on naphthyl-functionalized porphyrins, , to our knowledge, Figure a provides the first experimental structural characterization of an individual porphyrin fused with naphthalenes, representing archetypical polycyclic aromatic hydrocarbons.…”

“…38,53 Furthermore, such saddle-shaped macrocycle deformations are characteristic of functionalized porphyrins on Au(111) and Ag(111) surfaces. 54−56 Though there have been studies on naphthyl-functionalized porphyrins, 57,58 to our knowledge, Figure 1a provides the first experimental structural characterization of an individual porphyrin fused with naphthalenes, representing archetypical polycyclic aromatic hydrocarbons. The oligomerization is induced by debromination of the naphthalenes, followed by C−C aryl−aryl coupling.…”