Theoretical aspects of the reactivity of MN4 macrocyclics in electrochemical reactions

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

Resultado de la investigación: Chapter

1 Cita (Scopus)

Resumen

We studied the electronic features of different adsorption and catalytic processes of some transition metal macrocyclic complexes (phthalocyanine) with Fe being the usual metal center. For oxygen molecule on iron phthalocyanine (FePc), both end-on and side-on configurations are found to be energetically favorable. However, the end-on adsorption configurations are more stable than side-on configurations. The activation barrier for the O–O bind cleavage for the side-on MN4-O2 configuration is lower than that for the end-on MN4-O2 configuration. On the other hand, we have built theoretical models based on DFT calculations from the formation of self-assembled monolayers (SAM) on a gold substrate and a thiolate ligand as an “anchoring” fragment of metallophtalocyanine, which leads to an interesting charge donation from the 4-aminothiophenol (4-ATP), 4-MP (4-mercaptopyridine) and 1-(4-mercaptophenyl)-2, 6-diphenyl-4- (4-pyridyl)pyridinium tetrafluoroborate (MDPP) towards both gold substrate, Au(111) surface, and phthalocyanine, denoting an effective gold-MPc interaction mediated by the titled anchor ligands. The electrocatalytic studies carried out with Au/4-ATP/FePc and Au/MDPP/FePc electrodes show that the O2 reduction takes place by the transfer of 4-electron to give water in contrast to a 2-electron transfer process observed for the bare gold. Theoretical calculations suggest the importance of the backbonding mechanism into the adduct formation, showing the relevance of the supporting gold surface on the electron-transfer process mediated by anchoring ligands.

Idioma originalEnglish
Título de la publicación alojadaElectrochemistry of N4 Macrocyclic Metal Complexes
Subtítulo de la publicación alojadaVolume 1: Energy, Second Edition
EditorialSpringer International Publishing
Páginas143-170
Número de páginas28
ISBN (versión digital)9783319311722
ISBN (versión impresa)9783319311708
DOI
EstadoPublished - 1 ene 2016

Huella dactilar

Gold
Ligands
Electrons
Adsorption
Self assembled monolayers
Substrates
Metal complexes
Anchors
Discrete Fourier transforms
Transition metals
Metals
Chemical activation
Iron
Oxygen
Electrodes
Molecules
Water
4-aminothiophenol
2-methyl-1,1-diphenyl-3-(1-pyrrolidyl)-1-propanol
phthalocyanine

ASJC Scopus subject areas

  • Chemistry(all)
  • Engineering(all)
  • Chemical Engineering(all)

Citar esto

Miranda-Rojas, S., Muñoz-Castro, A., Arratia-Pérez, R., & Mendizábal, F. (2016). Theoretical aspects of the reactivity of MN4 macrocyclics in electrochemical reactions. En Electrochemistry of N4 Macrocyclic Metal Complexes: Volume 1: Energy, Second Edition (pp. 143-170). Springer International Publishing. https://doi.org/10.1007/978-3-319-31172-2_5
Miranda-Rojas, Sebastián ; Muñoz-Castro, Alvaro ; Arratia-Pérez, Ramiro ; Mendizábal, Fernando. / Theoretical aspects of the reactivity of MN4 macrocyclics in electrochemical reactions. Electrochemistry of N4 Macrocyclic Metal Complexes: Volume 1: Energy, Second Edition. Springer International Publishing, 2016. pp. 143-170
@inbook{f585f969c0664cf0ad4d9af861e7debf,
title = "Theoretical aspects of the reactivity of MN4 macrocyclics in electrochemical reactions",
abstract = "We studied the electronic features of different adsorption and catalytic processes of some transition metal macrocyclic complexes (phthalocyanine) with Fe being the usual metal center. For oxygen molecule on iron phthalocyanine (FePc), both end-on and side-on configurations are found to be energetically favorable. However, the end-on adsorption configurations are more stable than side-on configurations. The activation barrier for the O–O bind cleavage for the side-on MN4-O2 configuration is lower than that for the end-on MN4-O2 configuration. On the other hand, we have built theoretical models based on DFT calculations from the formation of self-assembled monolayers (SAM) on a gold substrate and a thiolate ligand as an “anchoring” fragment of metallophtalocyanine, which leads to an interesting charge donation from the 4-aminothiophenol (4-ATP), 4-MP (4-mercaptopyridine) and 1-(4-mercaptophenyl)-2, 6-diphenyl-4- (4-pyridyl)pyridinium tetrafluoroborate (MDPP) towards both gold substrate, Au(111) surface, and phthalocyanine, denoting an effective gold-MPc interaction mediated by the titled anchor ligands. The electrocatalytic studies carried out with Au/4-ATP/FePc and Au/MDPP/FePc electrodes show that the O2 reduction takes place by the transfer of 4-electron to give water in contrast to a 2-electron transfer process observed for the bare gold. Theoretical calculations suggest the importance of the backbonding mechanism into the adduct formation, showing the relevance of the supporting gold surface on the electron-transfer process mediated by anchoring ligands.",
author = "Sebasti{\'a}n Miranda-Rojas and Alvaro Mu{\~n}oz-Castro and Ramiro Arratia-P{\'e}rez and Fernando Mendiz{\'a}bal",
year = "2016",
month = "1",
day = "1",
doi = "10.1007/978-3-319-31172-2_5",
language = "English",
isbn = "9783319311708",
pages = "143--170",
booktitle = "Electrochemistry of N4 Macrocyclic Metal Complexes",
publisher = "Springer International Publishing",

}

Miranda-Rojas, S, Muñoz-Castro, A, Arratia-Pérez, R & Mendizábal, F 2016, Theoretical aspects of the reactivity of MN4 macrocyclics in electrochemical reactions. En Electrochemistry of N4 Macrocyclic Metal Complexes: Volume 1: Energy, Second Edition. Springer International Publishing, pp. 143-170. https://doi.org/10.1007/978-3-319-31172-2_5

Theoretical aspects of the reactivity of MN4 macrocyclics in electrochemical reactions. / Miranda-Rojas, Sebastián; Muñoz-Castro, Alvaro; Arratia-Pérez, Ramiro; Mendizábal, Fernando.

Electrochemistry of N4 Macrocyclic Metal Complexes: Volume 1: Energy, Second Edition. Springer International Publishing, 2016. p. 143-170.

Resultado de la investigación: Chapter

TY - CHAP

T1 - Theoretical aspects of the reactivity of MN4 macrocyclics in electrochemical reactions

AU - Miranda-Rojas, Sebastián

AU - Muñoz-Castro, Alvaro

AU - Arratia-Pérez, Ramiro

AU - Mendizábal, Fernando

PY - 2016/1/1

Y1 - 2016/1/1

N2 - We studied the electronic features of different adsorption and catalytic processes of some transition metal macrocyclic complexes (phthalocyanine) with Fe being the usual metal center. For oxygen molecule on iron phthalocyanine (FePc), both end-on and side-on configurations are found to be energetically favorable. However, the end-on adsorption configurations are more stable than side-on configurations. The activation barrier for the O–O bind cleavage for the side-on MN4-O2 configuration is lower than that for the end-on MN4-O2 configuration. On the other hand, we have built theoretical models based on DFT calculations from the formation of self-assembled monolayers (SAM) on a gold substrate and a thiolate ligand as an “anchoring” fragment of metallophtalocyanine, which leads to an interesting charge donation from the 4-aminothiophenol (4-ATP), 4-MP (4-mercaptopyridine) and 1-(4-mercaptophenyl)-2, 6-diphenyl-4- (4-pyridyl)pyridinium tetrafluoroborate (MDPP) towards both gold substrate, Au(111) surface, and phthalocyanine, denoting an effective gold-MPc interaction mediated by the titled anchor ligands. The electrocatalytic studies carried out with Au/4-ATP/FePc and Au/MDPP/FePc electrodes show that the O2 reduction takes place by the transfer of 4-electron to give water in contrast to a 2-electron transfer process observed for the bare gold. Theoretical calculations suggest the importance of the backbonding mechanism into the adduct formation, showing the relevance of the supporting gold surface on the electron-transfer process mediated by anchoring ligands.

AB - We studied the electronic features of different adsorption and catalytic processes of some transition metal macrocyclic complexes (phthalocyanine) with Fe being the usual metal center. For oxygen molecule on iron phthalocyanine (FePc), both end-on and side-on configurations are found to be energetically favorable. However, the end-on adsorption configurations are more stable than side-on configurations. The activation barrier for the O–O bind cleavage for the side-on MN4-O2 configuration is lower than that for the end-on MN4-O2 configuration. On the other hand, we have built theoretical models based on DFT calculations from the formation of self-assembled monolayers (SAM) on a gold substrate and a thiolate ligand as an “anchoring” fragment of metallophtalocyanine, which leads to an interesting charge donation from the 4-aminothiophenol (4-ATP), 4-MP (4-mercaptopyridine) and 1-(4-mercaptophenyl)-2, 6-diphenyl-4- (4-pyridyl)pyridinium tetrafluoroborate (MDPP) towards both gold substrate, Au(111) surface, and phthalocyanine, denoting an effective gold-MPc interaction mediated by the titled anchor ligands. The electrocatalytic studies carried out with Au/4-ATP/FePc and Au/MDPP/FePc electrodes show that the O2 reduction takes place by the transfer of 4-electron to give water in contrast to a 2-electron transfer process observed for the bare gold. Theoretical calculations suggest the importance of the backbonding mechanism into the adduct formation, showing the relevance of the supporting gold surface on the electron-transfer process mediated by anchoring ligands.

UR - http://www.scopus.com/inward/record.url?scp=84978193841&partnerID=8YFLogxK

U2 - 10.1007/978-3-319-31172-2_5

DO - 10.1007/978-3-319-31172-2_5

M3 - Chapter

SN - 9783319311708

SP - 143

EP - 170

BT - Electrochemistry of N4 Macrocyclic Metal Complexes

PB - Springer International Publishing

ER -

Miranda-Rojas S, Muñoz-Castro A, Arratia-Pérez R, Mendizábal F. Theoretical aspects of the reactivity of MN4 macrocyclics in electrochemical reactions. En Electrochemistry of N4 Macrocyclic Metal Complexes: Volume 1: Energy, Second Edition. Springer International Publishing. 2016. p. 143-170 https://doi.org/10.1007/978-3-319-31172-2_5