Order, disorder, and metalation of tetraphenylporphyrin (2H-TPP) on Au(111)

Abstract

A thermally induced order-disorder transition of tetraphenylporphyrin (2H-TPP) on Au(111) is characterised by a combination of scanning probe microscopy and X-ray photoelectron spectroscopy-based techniques. We observed that a transition from...

Molecular Diffusion and Self-Assembly: Quantifying the Influence of Substrate hcp and fcc Atomic Stacking

“…Indeed, when the Au reconstruction is locally disrupted, such that the area of the fcc region is increased, TPP islands fill this fcc region and exhibit an island aspect ratio closer to 1 (see SI) while still avoiding hcp regions. The internal structure of the islands are similar to that previously reported, with measured STM overlayer cell dimensions of 1.46 ± 0.05 nm × 1.49 ± 0.10 nm, 90 ± 3° (see SI for details) . Island growth is observed to extend into hcp regions, attributed to instances where the local availability of TPP molecules results in the saturation of the growth region area.…”

“…At very low coverages (∼0.04 ML), step-edge sites and point dislocations on type x solitons [the end point of atomic rows which are incorporated into the surface layer as part of the reconstruction; leading to Burgers circuits with nonzero Burgers vectors] are decorated with TPP (see Figure a and SI) with no close-packed structures observed. Increasing the coverage to ∼0.2 ML results in the formation of close-packed islands (as previously reported ,, ), the presence of individual TPP at nearly all point dislocation elbow sites of the herringbone reconstruction and, infrequently, within the fcc or hcp regions of the herringbone reconstruction (see Figure b).…”

“…The internal structure of the islands are similar to that previously reported, with measured STM overlayer cell dimensions of 1.46 ± 0.05 nm × 1.49 ± 0.10 nm, 90 ± 3°(see SI for details). 8 Island growth is observed to extend into hcp regions, attributed to instances where the local availability of TPP molecules results in the saturation of the growth region area. We postulate that angularly aligned islands in neighboring fcc regions may stabilize growth in the interstitial hcp regions.…”

“…Scanning probe microscopy (SPM) approaches allow on-surface processes to be studied on the single-molecule and single atom level, and studies utilizing non-contact atomic force microscopy (nc-AFM) have provided chemical-bond level resolution . In addition, SPM techniques combined with photoemission spectroscopies can provide detailed structural and chemical characterization of on-surface processes. − …”

Synthesis of extended covalently bound porphyrins on the Au(111) surface

“…Upon annealing to 167± 50 °C, they found evidence of metalation through XPS and scanning tunneling spectroscopy. 49 Additionally, evidence of Ullman-like coupling was seen at this annealing step and was circled in green showing the formation of a small COF, composed of TBrPP. The white dashed line in Fig.…”