Linker rectifiers for covalent attachment of transition-metal catalysts to metal-oxide surfaces

Wendu Ding, Christian F A Negre, Julio L. Palma, Alec C. Durrell, Laura J. Allen, Karin J. Young, Rebecca L. Milot, Charles A. Schmuttenmaer, Gary W Brudvig, Robert H. Crabtree, Victor S. Batista

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

Linkers that favor rectification of interfacial electron transfer are likely to be required for efficient photo-driven catalysis of multi-electron reactions at electrode surfaces. Design principles are discussed, together with the synthesis and characterization of a specific pair of molecular linkers, related by inversion of the direction of an amide bond in the heart of the molecule. The linkers have a terpyridyl group that can covalently bind Mn as in a well-known water oxidation catalyst and an acetylacetonate group that allows attachment to TiO2 surfaces. The appropriate choice of the sense of the amide linkage yields directionality of interfacial electron transfer, essential to enhance electron injection and slow back-electron transfer. Support comes from electron paramagnetic resonance and terahertz spectroscopic measurements, as well as computational modeling characterizing the asymmetry of electron transfer properties. Linker rectifiers induce directionality of interfacial electron transfer suitable for multi-electron reactions at electrode surfaces. The linkers have a terpyridyl group that can covalently bind Mn as in a well-known water oxidation catalyst and an acetylacetonate group that allows attachment to TiO2 surfaces. The appropriate choice of the sense of the amide linkage suppresses back-electron transfer by shifting the transport channel away from the Fermi level.

Original languageEnglish
Pages (from-to)1138-1147
Number of pages10
JournalChemPhysChem
Volume15
Issue number6
DOIs
Publication statusPublished - Apr 14 2014

Fingerprint

rectifiers
Oxides
Transition metals
attachment
metal oxides
electron transfer
Metals
transition metals
catalysts
Catalysts
Electrons
amides
Amides
linkages
oxidation
electrons
electrodes
rectification
Oxidation
water

Keywords

  • density functional theory
  • dye-sensitized solar cells
  • electron transport
  • molecular rectifier
  • photocatalysis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Ding, W., Negre, C. F. A., Palma, J. L., Durrell, A. C., Allen, L. J., Young, K. J., ... Batista, V. S. (2014). Linker rectifiers for covalent attachment of transition-metal catalysts to metal-oxide surfaces. ChemPhysChem, 15(6), 1138-1147. https://doi.org/10.1002/cphc.201400063

Linker rectifiers for covalent attachment of transition-metal catalysts to metal-oxide surfaces. / Ding, Wendu; Negre, Christian F A; Palma, Julio L.; Durrell, Alec C.; Allen, Laura J.; Young, Karin J.; Milot, Rebecca L.; Schmuttenmaer, Charles A.; Brudvig, Gary W; Crabtree, Robert H.; Batista, Victor S.

In: ChemPhysChem, Vol. 15, No. 6, 14.04.2014, p. 1138-1147.

Research output: Contribution to journalArticle

Ding, W, Negre, CFA, Palma, JL, Durrell, AC, Allen, LJ, Young, KJ, Milot, RL, Schmuttenmaer, CA, Brudvig, GW, Crabtree, RH & Batista, VS 2014, 'Linker rectifiers for covalent attachment of transition-metal catalysts to metal-oxide surfaces', ChemPhysChem, vol. 15, no. 6, pp. 1138-1147. https://doi.org/10.1002/cphc.201400063
Ding W, Negre CFA, Palma JL, Durrell AC, Allen LJ, Young KJ et al. Linker rectifiers for covalent attachment of transition-metal catalysts to metal-oxide surfaces. ChemPhysChem. 2014 Apr 14;15(6):1138-1147. https://doi.org/10.1002/cphc.201400063
Ding, Wendu ; Negre, Christian F A ; Palma, Julio L. ; Durrell, Alec C. ; Allen, Laura J. ; Young, Karin J. ; Milot, Rebecca L. ; Schmuttenmaer, Charles A. ; Brudvig, Gary W ; Crabtree, Robert H. ; Batista, Victor S. / Linker rectifiers for covalent attachment of transition-metal catalysts to metal-oxide surfaces. In: ChemPhysChem. 2014 ; Vol. 15, No. 6. pp. 1138-1147.
@article{dbc10fe6a97b4273974623c7de3af8c5,
title = "Linker rectifiers for covalent attachment of transition-metal catalysts to metal-oxide surfaces",
abstract = "Linkers that favor rectification of interfacial electron transfer are likely to be required for efficient photo-driven catalysis of multi-electron reactions at electrode surfaces. Design principles are discussed, together with the synthesis and characterization of a specific pair of molecular linkers, related by inversion of the direction of an amide bond in the heart of the molecule. The linkers have a terpyridyl group that can covalently bind Mn as in a well-known water oxidation catalyst and an acetylacetonate group that allows attachment to TiO2 surfaces. The appropriate choice of the sense of the amide linkage yields directionality of interfacial electron transfer, essential to enhance electron injection and slow back-electron transfer. Support comes from electron paramagnetic resonance and terahertz spectroscopic measurements, as well as computational modeling characterizing the asymmetry of electron transfer properties. Linker rectifiers induce directionality of interfacial electron transfer suitable for multi-electron reactions at electrode surfaces. The linkers have a terpyridyl group that can covalently bind Mn as in a well-known water oxidation catalyst and an acetylacetonate group that allows attachment to TiO2 surfaces. The appropriate choice of the sense of the amide linkage suppresses back-electron transfer by shifting the transport channel away from the Fermi level.",
keywords = "density functional theory, dye-sensitized solar cells, electron transport, molecular rectifier, photocatalysis",
author = "Wendu Ding and Negre, {Christian F A} and Palma, {Julio L.} and Durrell, {Alec C.} and Allen, {Laura J.} and Young, {Karin J.} and Milot, {Rebecca L.} and Schmuttenmaer, {Charles A.} and Brudvig, {Gary W} and Crabtree, {Robert H.} and Batista, {Victor S.}",
year = "2014",
month = "4",
day = "14",
doi = "10.1002/cphc.201400063",
language = "English",
volume = "15",
pages = "1138--1147",
journal = "ChemPhysChem",
issn = "1439-4235",
publisher = "Wiley-VCH Verlag",
number = "6",

}

TY - JOUR

T1 - Linker rectifiers for covalent attachment of transition-metal catalysts to metal-oxide surfaces

AU - Ding, Wendu

AU - Negre, Christian F A

AU - Palma, Julio L.

AU - Durrell, Alec C.

AU - Allen, Laura J.

AU - Young, Karin J.

AU - Milot, Rebecca L.

AU - Schmuttenmaer, Charles A.

AU - Brudvig, Gary W

AU - Crabtree, Robert H.

AU - Batista, Victor S.

PY - 2014/4/14

Y1 - 2014/4/14

N2 - Linkers that favor rectification of interfacial electron transfer are likely to be required for efficient photo-driven catalysis of multi-electron reactions at electrode surfaces. Design principles are discussed, together with the synthesis and characterization of a specific pair of molecular linkers, related by inversion of the direction of an amide bond in the heart of the molecule. The linkers have a terpyridyl group that can covalently bind Mn as in a well-known water oxidation catalyst and an acetylacetonate group that allows attachment to TiO2 surfaces. The appropriate choice of the sense of the amide linkage yields directionality of interfacial electron transfer, essential to enhance electron injection and slow back-electron transfer. Support comes from electron paramagnetic resonance and terahertz spectroscopic measurements, as well as computational modeling characterizing the asymmetry of electron transfer properties. Linker rectifiers induce directionality of interfacial electron transfer suitable for multi-electron reactions at electrode surfaces. The linkers have a terpyridyl group that can covalently bind Mn as in a well-known water oxidation catalyst and an acetylacetonate group that allows attachment to TiO2 surfaces. The appropriate choice of the sense of the amide linkage suppresses back-electron transfer by shifting the transport channel away from the Fermi level.

AB - Linkers that favor rectification of interfacial electron transfer are likely to be required for efficient photo-driven catalysis of multi-electron reactions at electrode surfaces. Design principles are discussed, together with the synthesis and characterization of a specific pair of molecular linkers, related by inversion of the direction of an amide bond in the heart of the molecule. The linkers have a terpyridyl group that can covalently bind Mn as in a well-known water oxidation catalyst and an acetylacetonate group that allows attachment to TiO2 surfaces. The appropriate choice of the sense of the amide linkage yields directionality of interfacial electron transfer, essential to enhance electron injection and slow back-electron transfer. Support comes from electron paramagnetic resonance and terahertz spectroscopic measurements, as well as computational modeling characterizing the asymmetry of electron transfer properties. Linker rectifiers induce directionality of interfacial electron transfer suitable for multi-electron reactions at electrode surfaces. The linkers have a terpyridyl group that can covalently bind Mn as in a well-known water oxidation catalyst and an acetylacetonate group that allows attachment to TiO2 surfaces. The appropriate choice of the sense of the amide linkage suppresses back-electron transfer by shifting the transport channel away from the Fermi level.

KW - density functional theory

KW - dye-sensitized solar cells

KW - electron transport

KW - molecular rectifier

KW - photocatalysis

UR - http://www.scopus.com/inward/record.url?scp=84898882479&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84898882479&partnerID=8YFLogxK

U2 - 10.1002/cphc.201400063

DO - 10.1002/cphc.201400063

M3 - Article

VL - 15

SP - 1138

EP - 1147

JO - ChemPhysChem

JF - ChemPhysChem

SN - 1439-4235

IS - 6

ER -