Role of Deprotonation and Cu Adatom Migration in Determining the Reaction Pathways of Oxalic Acid Adsorption on Cu(111)

Faraggi, Marisa N.; Rogero, Celia; Arnau, A.; Trelka, Marta; Écija, David; Isvoranu, Cristina; Schnadt, Joachim; Martí‐Gastaldo, Carlos; Coronado, Eugenio; Gallego, José M.; Otero, Roberto; Miranda, Rodolfo

doi:10.1021/jp205779g

Cited by 22 publications

(24 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Figure 2 b displays an STM image taken for a sample which was annealed at 385 K. The porous network structure disappeared and only the same close-packed structure already observed for room temperature preparation is present. It can be concluded, in accordance with what is reported for related molecules, 29 − 32 that the deprotonation process is enhanced upon annealing. For annealing BTB on Cu(111) at 385 K all molecules are deprotonated and thus, the close-packed structure is the only structure present after annealing.…”

Section: Resultssupporting

confidence: 91%

“…Studies on related molecules having carboxylic acid end groups showed that the hydroxyl groups get deprotonated upon deposition on Cu surfaces. 29−32 Therefore, we suggest that the BTB molecules in the close-packed structure are deprotonated. The deprotonated carboxylic acid groups point to the center of neighboring BTB molecules and two hydrogen bonds are formed between the oxygen atoms of the COO group and hydrogen atoms of neighboring CH groups (see structure model in Figure 2d).…”

Section: Resultsmentioning

confidence: 88%

See 1 more Smart Citation

1,3,5-Benzenetribenzoic Acid on Cu(111) and Graphene/Cu(111): A Comparative STM Study

Gottardi

Solianyk

et al. 2016

J. Phys. Chem. C

View full text Add to dashboard Cite

The self-assembly of 1,3,5-benzenetribenzoic acid (BTB) molecules on both Cu(111) and epitaxial graphene grown on Cu(111) were studied by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) under ultrahigh vacuum conditions. On Cu(111), the BTB molecules were found to mainly arrange in close-packed structures through H-bonding between the (partially) deprotonated carboxylic acid groups. In addition, porous structures formed by intact BTB molecules-and also based on H-bonding-were observed. On graphene grown on Cu(111) the BTB molecules mainly form porous structures accompanied by small patches of disordered close-packed structures. Upon annealing, BTB adsorbed on Cu(111) is fully deprotonated and arranges in the close-packed structure while in contrast on graphene/Cu(111) the porous network is exclusively formed. This shows that the molecular self-assembly behavior is highly dependent on the first substrate layer: one graphene layer is sufficient to considerably alter the interplay of molecule substrate and intermolecular interactions in favor of the latter interactions.

show abstract

Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 88%

1,3,5-Benzenetribenzoic Acid on Cu(111) and Graphene/Cu(111): A Comparative STM Study

Gottardi

Solianyk

et al. 2016

J. Phys. Chem. C

View full text Add to dashboard Cite

show abstract

“…This result is also important because of the small size of TCNE. TCNE is one of the smallest molecules involved in metal organic coordination networks (together with the carboxylic acid C 2 O 4 H 2 ), 31,32 and therefore able to provide a rather short metal-to-metal distance. This is probably involved in the magnetic properties that have been reported for TCNE metal-coordination networks, with metalmetal distances between 7 and 10 Å.…”

Section: Discussionmentioning

confidence: 99%

Temperature-controlled metal/ligand stoichiometric ratio in Ag-TCNE coordination networks

Rodrı́guez-Fernández

Lauwaet

Herranz

et al. 2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

The deposition of tetracyanoethylene (TCNE) on Ag(111), both at Room Temperature (RT, 300 K) and low temperatures (150 K), leads to the formation of coordination networks involving silver adatoms, as revealed by Variable-Temperature Scanning Tunneling Microscopy. Our results indicate that TCNE molecules etch away material from the step edges and possibly also from the terraces, which facilitates the formation of the observed coordination networks. Moreover, such process is temperature dependent, which allows for different stoichiometric ratios between Ag and TCNE just by adjusting the deposition temperature. X-ray Photoelectron Spectroscopy and Density Functional Theory calculations reveal that charge-transfer from the surface to the molecule and the concomitant geometrical distortions at both sides of the organic/inorganic interface might facilitate the extraction of silver atoms from the step-edges and, thus, its incorporation into the observed TCNE coordination networks. C 2015 AIP Publishing LLC. [http://dx

show abstract

“…[15][16][17][18] Notably, a wide variety of different molecules, including 1,3,5-tris(4-mercaptophenyl)benzene (TMB), 1,3,8,10-tetrazaperopyrene (TAPP), oxalic acid, among many others deprotonate upon adsorption to crystalline Cu, which for carboxyl groups is known to be catalyzed by the lattice gas of Cu adatoms. [19][20][21] Once deprotonated, molecules often form metal coordination bonds with the present Cu adatoms, which was demonstrated conclusively for trimesic acid (TMA). 15 Some of these molecules require thermal activation in order to deprotonate.…”

mentioning

confidence: 87%

Rhodizonic Acid on Noble Metals: Surface Reactivity and Coordination Chemistry

Kunkel

Hooper

Simpson

et al. 2013

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

A study of the two-dimensional crystallization of rhodizonic acid on the crystalline surfaces of gold and copper is presented. Rhodizonic acid, a cyclic oxocarbon related to the ferroelectric croconic acid and the antiferroelectric squaric acid, has not been synthesized in bulk crystalline form yet. Capitalizing on surface-assisted molecular selfassembly, a two-dimensional analogue to the well-known solution-based coordination chemistry, two-dimensional structures of rhodizonic acid were stabilized under ultrahigh vacuum on Au(111) and Cu(111) surfaces. Scanning tunneling microscopy, coupled with first-principles calculations, reveals that on the less reactive Au surface, extended twodimensional islands of rhodizonic acid are formed, in which the molecules interact via hydrogen bonding and dispersion forces. However, the rhodizonic acid deprotonates into rhodizonate on Cu substrates upon annealing, forming magic clusters and metal−organic coordination networks with substrate adatoms. The networks show a 2:1 distribution of rhodizonate coordinated with 3 and 6 Cu atoms, respectively. The stabilization of crystalline structures of rhodizonic acid, structures not reported before, and their transition into metal−organic networks demonstrate the potential of surface chemistry to synthesize new and potential useful organic nanomaterials.

show abstract

Role of Deprotonation and Cu Adatom Migration in Determining the Reaction Pathways of Oxalic Acid Adsorption on Cu(111)

Cited by 22 publications

References 43 publications

1,3,5-Benzenetribenzoic Acid on Cu(111) and Graphene/Cu(111): A Comparative STM Study

1,3,5-Benzenetribenzoic Acid on Cu(111) and Graphene/Cu(111): A Comparative STM Study

Temperature-controlled metal/ligand stoichiometric ratio in Ag-TCNE coordination networks

Rhodizonic Acid on Noble Metals: Surface Reactivity and Coordination Chemistry

Contact Info

Product

Resources

About