Subtle changes to peripheral ligands enable high turnover numbers for photocatalytic hydrogen generation with supramolecular photocatalysts

T. Kowacs, L. O'Reilly, Qing Pan, Jannetje Maria Huijser, P. Lang, S. Rau, W.R. Browne, M.T. Pryce, J.G. Vos

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Abstract

The photocatalytic generation of hydrogen (H2) from protons by two cyclometalated ruthenium–platinum polypyridyl complexes, [Ru(bpy)2(2,5-bpp)PtIS]2+ (1) and [Ru(dceb)2(2,5-bpp)PtIS]2+ (2) [where bpy = 2,2′-bipyridine, 2,5-bpp = 2,2′,5′,2″-terpyridine, dceb = 4,4′-di(carboxyethyl)bipyridine, and S = solvent], is reported. Turnover numbers (TONs) for H2 generation were increased by nearly an order of magnitude by the introduction of carboxyethyl ester units, i.e., from 80 for 1P to 650 for 2P after 6 h of irradiation, with an early turnover frequency (TOF) increasing from 15 to 200 h–1. The TON and TOF values for 2P are among the highest reported to date for supramolecular photocatalysts. The increase correlates with stabilization of the excited states localized on the peripheral ligands of the light-harvesting RuII center.
Original languageEnglish
Pages (from-to)2685-2690
JournalInorganic chemistry
Volume55
Issue number6
DOIs
Publication statusPublished - 2016

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Photocatalysts
Excited states
Protons
Hydrogen
Esters
Stabilization
Irradiation
Ligands
ligands
hydrogen
esters
stabilization
irradiation
protons
excitation
bis(bipyridyl)ruthenium(II)

Keywords

  • IR-101157
  • METIS-316335

Cite this

Kowacs, T. ; O'Reilly, L. ; Pan, Qing ; Huijser, Jannetje Maria ; Lang, P. ; Rau, S. ; Browne, W.R. ; Pryce, M.T. ; Vos, J.G. / Subtle changes to peripheral ligands enable high turnover numbers for photocatalytic hydrogen generation with supramolecular photocatalysts. In: Inorganic chemistry. 2016 ; Vol. 55, No. 6. pp. 2685-2690.
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abstract = "The photocatalytic generation of hydrogen (H2) from protons by two cyclometalated ruthenium–platinum polypyridyl complexes, [Ru(bpy)2(2,5-bpp)PtIS]2+ (1) and [Ru(dceb)2(2,5-bpp)PtIS]2+ (2) [where bpy = 2,2′-bipyridine, 2,5-bpp = 2,2′,5′,2″-terpyridine, dceb = 4,4′-di(carboxyethyl)bipyridine, and S = solvent], is reported. Turnover numbers (TONs) for H2 generation were increased by nearly an order of magnitude by the introduction of carboxyethyl ester units, i.e., from 80 for 1P to 650 for 2P after 6 h of irradiation, with an early turnover frequency (TOF) increasing from 15 to 200 h–1. The TON and TOF values for 2P are among the highest reported to date for supramolecular photocatalysts. The increase correlates with stabilization of the excited states localized on the peripheral ligands of the light-harvesting RuII center.",
keywords = "IR-101157, METIS-316335",
author = "T. Kowacs and L. O'Reilly and Qing Pan and Huijser, {Jannetje Maria} and P. Lang and S. Rau and W.R. Browne and M.T. Pryce and J.G. Vos",
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doi = "10.1021/acs.inorgchem.5b01752",
language = "English",
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Subtle changes to peripheral ligands enable high turnover numbers for photocatalytic hydrogen generation with supramolecular photocatalysts. / Kowacs, T.; O'Reilly, L.; Pan, Qing; Huijser, Jannetje Maria; Lang, P.; Rau, S.; Browne, W.R.; Pryce, M.T.; Vos, J.G.

In: Inorganic chemistry, Vol. 55, No. 6, 2016, p. 2685-2690.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Subtle changes to peripheral ligands enable high turnover numbers for photocatalytic hydrogen generation with supramolecular photocatalysts

AU - Kowacs, T.

AU - O'Reilly, L.

AU - Pan, Qing

AU - Huijser, Jannetje Maria

AU - Lang, P.

AU - Rau, S.

AU - Browne, W.R.

AU - Pryce, M.T.

AU - Vos, J.G.

PY - 2016

Y1 - 2016

N2 - The photocatalytic generation of hydrogen (H2) from protons by two cyclometalated ruthenium–platinum polypyridyl complexes, [Ru(bpy)2(2,5-bpp)PtIS]2+ (1) and [Ru(dceb)2(2,5-bpp)PtIS]2+ (2) [where bpy = 2,2′-bipyridine, 2,5-bpp = 2,2′,5′,2″-terpyridine, dceb = 4,4′-di(carboxyethyl)bipyridine, and S = solvent], is reported. Turnover numbers (TONs) for H2 generation were increased by nearly an order of magnitude by the introduction of carboxyethyl ester units, i.e., from 80 for 1P to 650 for 2P after 6 h of irradiation, with an early turnover frequency (TOF) increasing from 15 to 200 h–1. The TON and TOF values for 2P are among the highest reported to date for supramolecular photocatalysts. The increase correlates with stabilization of the excited states localized on the peripheral ligands of the light-harvesting RuII center.

AB - The photocatalytic generation of hydrogen (H2) from protons by two cyclometalated ruthenium–platinum polypyridyl complexes, [Ru(bpy)2(2,5-bpp)PtIS]2+ (1) and [Ru(dceb)2(2,5-bpp)PtIS]2+ (2) [where bpy = 2,2′-bipyridine, 2,5-bpp = 2,2′,5′,2″-terpyridine, dceb = 4,4′-di(carboxyethyl)bipyridine, and S = solvent], is reported. Turnover numbers (TONs) for H2 generation were increased by nearly an order of magnitude by the introduction of carboxyethyl ester units, i.e., from 80 for 1P to 650 for 2P after 6 h of irradiation, with an early turnover frequency (TOF) increasing from 15 to 200 h–1. The TON and TOF values for 2P are among the highest reported to date for supramolecular photocatalysts. The increase correlates with stabilization of the excited states localized on the peripheral ligands of the light-harvesting RuII center.

KW - IR-101157

KW - METIS-316335

U2 - 10.1021/acs.inorgchem.5b01752

DO - 10.1021/acs.inorgchem.5b01752

M3 - Article

VL - 55

SP - 2685

EP - 2690

JO - Inorganic chemistry

JF - Inorganic chemistry

SN - 0020-1669

IS - 6

ER -