Theoretical insights into the adsorption of neutral, radical and anionic thiophenols on gold(111)

S. Miranda-Rojas, Alvaro Muñoz-Castro, Ramiro Arratia-Pérez, Fernando Mendizábal

Resultado de la investigación: Article

15 Citas (Scopus)

Resumen

The interaction of thiol and thiolate containing molecules with gold (S-Au) has gained increasing interest because of its applications in molecular electronic devices and catalysis. In this context, the enhanced conductivity of thiophenol compared to alkanethiol represents an opportunity to develop more sensitive and selective gold-based devices by incorporating molecules with the aryl-thiol moiety into their structures. As has been proposed earlier, the thiol moiety is deprotonated after binding to gold, hence, we present here a comparative study of the S-Au bond strength between several neutral and deprotonated aromatic-sulfur systems in their anionic and radical forms with a detailed description of the nature of this interaction. The study was performed by means of computational chemistry methods, using a cluster of 42 Au atoms as a model of the Au(111) surface that allowed us to provide new chemical insights to control the S-Au interface interaction strength. Our results revealed that the thiophenols-gold interaction is mainly dispersive where the interaction energies range between 31 and 43 kcal mol-1. The radical and anionic thiophenolates-gold interaction increases due to a strong charge transfer character, depicting interaction energies in the range of 50 to 55 kcal mol -1 and 62 to 92 kcal mol-1, respectively. These results suggest that for the anionic thiophenolate the binding strength can be tailored according to the electron-donor capabilities of the ligand which in turn can be finely tuned by several substituents. Our results are of possible impact for the design of new devices.

Idioma originalEnglish
Páginas (desde-hasta)20363-20370
Número de páginas8
PublicaciónPhysical Chemistry Chemical Physics
Volumen15
N.º46
DOI
EstadoPublished - 14 dic 2013

Huella dactilar

Gold
gold
Adsorption
adsorption
Sulfhydryl Compounds
thiols
interactions
Computational chemistry
Molecular electronics
Molecules
Sulfur
computational chemistry
Catalysis
Charge transfer
molecular electronics
thiophenol
Ligands
catalysis
Atoms
molecules

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Citar esto

@article{c2619e363c5d4468b8824dbaebe2ed73,
title = "Theoretical insights into the adsorption of neutral, radical and anionic thiophenols on gold(111)",
abstract = "The interaction of thiol and thiolate containing molecules with gold (S-Au) has gained increasing interest because of its applications in molecular electronic devices and catalysis. In this context, the enhanced conductivity of thiophenol compared to alkanethiol represents an opportunity to develop more sensitive and selective gold-based devices by incorporating molecules with the aryl-thiol moiety into their structures. As has been proposed earlier, the thiol moiety is deprotonated after binding to gold, hence, we present here a comparative study of the S-Au bond strength between several neutral and deprotonated aromatic-sulfur systems in their anionic and radical forms with a detailed description of the nature of this interaction. The study was performed by means of computational chemistry methods, using a cluster of 42 Au atoms as a model of the Au(111) surface that allowed us to provide new chemical insights to control the S-Au interface interaction strength. Our results revealed that the thiophenols-gold interaction is mainly dispersive where the interaction energies range between 31 and 43 kcal mol-1. The radical and anionic thiophenolates-gold interaction increases due to a strong charge transfer character, depicting interaction energies in the range of 50 to 55 kcal mol -1 and 62 to 92 kcal mol-1, respectively. These results suggest that for the anionic thiophenolate the binding strength can be tailored according to the electron-donor capabilities of the ligand which in turn can be finely tuned by several substituents. Our results are of possible impact for the design of new devices.",
author = "S. Miranda-Rojas and Alvaro Mu{\~n}oz-Castro and Ramiro Arratia-P{\'e}rez and Fernando Mendiz{\'a}bal",
year = "2013",
month = "12",
day = "14",
doi = "10.1039/c3cp53591f",
language = "English",
volume = "15",
pages = "20363--20370",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "46",

}

Theoretical insights into the adsorption of neutral, radical and anionic thiophenols on gold(111). / Miranda-Rojas, S.; Muñoz-Castro, Alvaro; Arratia-Pérez, Ramiro; Mendizábal, Fernando.

En: Physical Chemistry Chemical Physics, Vol. 15, N.º 46, 14.12.2013, p. 20363-20370.

Resultado de la investigación: Article

TY - JOUR

T1 - Theoretical insights into the adsorption of neutral, radical and anionic thiophenols on gold(111)

AU - Miranda-Rojas, S.

AU - Muñoz-Castro, Alvaro

AU - Arratia-Pérez, Ramiro

AU - Mendizábal, Fernando

PY - 2013/12/14

Y1 - 2013/12/14

N2 - The interaction of thiol and thiolate containing molecules with gold (S-Au) has gained increasing interest because of its applications in molecular electronic devices and catalysis. In this context, the enhanced conductivity of thiophenol compared to alkanethiol represents an opportunity to develop more sensitive and selective gold-based devices by incorporating molecules with the aryl-thiol moiety into their structures. As has been proposed earlier, the thiol moiety is deprotonated after binding to gold, hence, we present here a comparative study of the S-Au bond strength between several neutral and deprotonated aromatic-sulfur systems in their anionic and radical forms with a detailed description of the nature of this interaction. The study was performed by means of computational chemistry methods, using a cluster of 42 Au atoms as a model of the Au(111) surface that allowed us to provide new chemical insights to control the S-Au interface interaction strength. Our results revealed that the thiophenols-gold interaction is mainly dispersive where the interaction energies range between 31 and 43 kcal mol-1. The radical and anionic thiophenolates-gold interaction increases due to a strong charge transfer character, depicting interaction energies in the range of 50 to 55 kcal mol -1 and 62 to 92 kcal mol-1, respectively. These results suggest that for the anionic thiophenolate the binding strength can be tailored according to the electron-donor capabilities of the ligand which in turn can be finely tuned by several substituents. Our results are of possible impact for the design of new devices.

AB - The interaction of thiol and thiolate containing molecules with gold (S-Au) has gained increasing interest because of its applications in molecular electronic devices and catalysis. In this context, the enhanced conductivity of thiophenol compared to alkanethiol represents an opportunity to develop more sensitive and selective gold-based devices by incorporating molecules with the aryl-thiol moiety into their structures. As has been proposed earlier, the thiol moiety is deprotonated after binding to gold, hence, we present here a comparative study of the S-Au bond strength between several neutral and deprotonated aromatic-sulfur systems in their anionic and radical forms with a detailed description of the nature of this interaction. The study was performed by means of computational chemistry methods, using a cluster of 42 Au atoms as a model of the Au(111) surface that allowed us to provide new chemical insights to control the S-Au interface interaction strength. Our results revealed that the thiophenols-gold interaction is mainly dispersive where the interaction energies range between 31 and 43 kcal mol-1. The radical and anionic thiophenolates-gold interaction increases due to a strong charge transfer character, depicting interaction energies in the range of 50 to 55 kcal mol -1 and 62 to 92 kcal mol-1, respectively. These results suggest that for the anionic thiophenolate the binding strength can be tailored according to the electron-donor capabilities of the ligand which in turn can be finely tuned by several substituents. Our results are of possible impact for the design of new devices.

UR - http://www.scopus.com/inward/record.url?scp=84888321915&partnerID=8YFLogxK

U2 - 10.1039/c3cp53591f

DO - 10.1039/c3cp53591f

M3 - Article

C2 - 24173319

AN - SCOPUS:84888321915

VL - 15

SP - 20363

EP - 20370

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 46

ER -