Abstract
We present a combined scanning tunneling microscopy (STM), near-edge x-ray-absorption fine-structure, and x-ray photoemission spectroscopy (XPS) study on the bonding and ordering of tetrapyridyl-porphyrin molecules on the Cu(111) surface in the 300-500 K temperature range. Following deposition at 300 K the molecules are adsorbed with a pronounced conformational adaptation of the anchored species featuring a saddle-shaped macrocycle and terminal groups pointing toward the substrate. Upon moderate annealing supramolecular chains evolve that are stabilized by metal-ligand interactions between the mesopyridyl substituents and copper adatoms resulting in twofold copper coordination. Annealing to temperatures exceeding 450 K strongly alters the molecular appearance in high-resolution STM data. This modification was also induced by controlled voltage pulses and related to a deprotonation of the molecule by XPS. Under appropriate conditions a novel binding motif leads to honeycomb structures coexisting with the chain segments. The conformation withstands annealing without large modification.
| Original language | English |
|---|---|
| Article number | 214702 |
| Journal | Journal of Chemical Physics |
| Volume | 129 |
| Issue number | 21 |
| DOIs | |
| Publication status | Published - 2008 |
| Externally published | Yes |
Cite this
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Temperature dependence of conformation, chemical state, and metal-directed assembly of tetrapyridyl-porphyrin on Cu(111). / Klappenberger, F.; Weber-Bargioni, A.; Auwärter, W.; Marschall, M.; Schiffrin, A.; Barth, J. V.
In: Journal of Chemical Physics, Vol. 129, No. 21, 214702, 2008.Research output: Contribution to journal › Article › Other
TY - JOUR
T1 - Temperature dependence of conformation, chemical state, and metal-directed assembly of tetrapyridyl-porphyrin on Cu(111)
AU - Klappenberger, F.
AU - Weber-Bargioni, A.
AU - Auwärter, W.
AU - Marschall, M.
AU - Schiffrin, A.
AU - Barth, J. V.
PY - 2008
Y1 - 2008
N2 - We present a combined scanning tunneling microscopy (STM), near-edge x-ray-absorption fine-structure, and x-ray photoemission spectroscopy (XPS) study on the bonding and ordering of tetrapyridyl-porphyrin molecules on the Cu(111) surface in the 300-500 K temperature range. Following deposition at 300 K the molecules are adsorbed with a pronounced conformational adaptation of the anchored species featuring a saddle-shaped macrocycle and terminal groups pointing toward the substrate. Upon moderate annealing supramolecular chains evolve that are stabilized by metal-ligand interactions between the mesopyridyl substituents and copper adatoms resulting in twofold copper coordination. Annealing to temperatures exceeding 450 K strongly alters the molecular appearance in high-resolution STM data. This modification was also induced by controlled voltage pulses and related to a deprotonation of the molecule by XPS. Under appropriate conditions a novel binding motif leads to honeycomb structures coexisting with the chain segments. The conformation withstands annealing without large modification.
AB - We present a combined scanning tunneling microscopy (STM), near-edge x-ray-absorption fine-structure, and x-ray photoemission spectroscopy (XPS) study on the bonding and ordering of tetrapyridyl-porphyrin molecules on the Cu(111) surface in the 300-500 K temperature range. Following deposition at 300 K the molecules are adsorbed with a pronounced conformational adaptation of the anchored species featuring a saddle-shaped macrocycle and terminal groups pointing toward the substrate. Upon moderate annealing supramolecular chains evolve that are stabilized by metal-ligand interactions between the mesopyridyl substituents and copper adatoms resulting in twofold copper coordination. Annealing to temperatures exceeding 450 K strongly alters the molecular appearance in high-resolution STM data. This modification was also induced by controlled voltage pulses and related to a deprotonation of the molecule by XPS. Under appropriate conditions a novel binding motif leads to honeycomb structures coexisting with the chain segments. The conformation withstands annealing without large modification.
UR - http://www.scopus.com/inward/record.url?scp=57349087337&partnerID=8YFLogxK
U2 - 10.1063/1.3021291
DO - 10.1063/1.3021291
M3 - Article
VL - 129
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 21
M1 - 214702
ER -