Photoinduced electron transfer in tris(2,2′-bipyridine)ruthenium(ii)- viologen dyads with peptide backbones leading to long-lived charge separation and hydrogen evolution

Makoto Ogawa, Bijitha Balan, Gopalakrishnan Ajayakumar, Shigeyuki Masaoka, Heinz Bernhard Kraatz, Masayasu Muramatsu, Syoji Ito, Yutaka Nagasawa, Hiroshi Miyasaka, Ken Sakai

研究成果: ジャーナルへの寄稿記事

29 引用 (Scopus)

抄録

Three 5,5′-disubstituted-2,2′-bipyridine ligands tethered to l-Asp-based peptide backbones having pendant viologen-modified branches, i.e., 5-ethoxycarbonyl-5′-(N-G1-carbamoyl)-2,2′-bipyridine (MV24+), 5,5′-bis(N-G1-carbamoyl)-2,2′- bipyridine (MV48+), and 5,5′-bis(N-G2-carbamoyl)-2, 2′-bipyridine (MV612+), were prepared, where G1 = Asp(NHG3)-NHG3, G2 = Asp(NHG 3)-Asp(NHG3)-NHG3, and G3 = -(CH2)2-+NC5H4-C 5H4N+-CH3, i.e., 2-(1′-methyl-4,4′-bipyridinediium-1-yl)ethyl. These were reacted with cis-Ru(bpy)2Cl2 to give three new dyads [Ru(bpy) 2(MV2)]6+ (RuMV26+), [Ru(bpy) 2(MV4)]10+ (RuMV410+), and [Ru(bpy) 2(MV6)]14+ (RuMV614+), respectively, where bpy = 2,2′-bipyridine. All these dyads undergo extremely efficient intramolecular quenching leading to the formation of charge separated (CS) states (RuIII-MV+), and display a triple exponential decay due to the presence of three classes of conformers with each exhibiting the individual rate of electron transfer. The lifetimes (contributions) were determined as 12.5 ps (94.2%), 791 ps (4.5%), and 18.3 ns (1.2%) for RuMV2, 82.2 ps (79.9%), 1.12 ns (12.4%), and 4.60 ns (7.7%) for RuMV4, and 43.6 ps (71.6%), 593 ps (20.2%), and 3.75 ns (8.1%) for RuMV6. The forward electron transfer rate constants (kET) for the major components were calculated as kET = 8.3 × 1010 s-1 for RuMV2, k ET = 1.2 × 1010 s-1 for RuMV4, and k ET = 2.3 × 1010 s-1 for RuMV6. Further, the lifetimes and quantum yields of charge separated states were determined as τCS = 16 ± 3 ns and ΦCS = 0.81 for RuMV2, τCS = 20 ± 3 ns and ΦCS = 0.92 for RuMV4, and τCS = 20 ± 3 ns and ΦCS = 0.64 for RuMV6. The backward electron transfer rate constants (kBET) were also determined as 6.3 × 107, 5.0 × 107, and 5.0 × 107 s-1 for RuMV2, RuMV4, and RuMV6, respectively. From the analysis of electrical conductivity, the major ion-pair adducts in aqueous media were characterized as RuMV2(PF6)5+ (52%) for RuMV2, RuMV4(PF6)28+ (29%) and RuMV4(PF 6)37+ (32%) for RuMV4, and RuMV6(PF 6)311+ (27%) and RuMV6(PF6) 410+ (29%) for RuMV6, at a total complex concentration of 0.04 mM. The present family is found to be the first example of a Ru(bpy) 32+-MV2+ system in which three orders of magnitude of difference is achieved between the forward and backward electron transfer rate constants. These dyads were finally combined with a Pt(ii)-based H2-evolving catalyst, i.e., cis-diamminedichloroplatinum(ii), to ascertain the applicability of the system towards the visible light-induced water splitting processes.

元の言語英語
ページ(範囲)4421-4434
ページ数14
ジャーナルDalton Transactions
39
発行部数18
DOI
出版物ステータス出版済み - 5 3 2010

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Viologens
Ruthenium
Hydrogen
Rate constants
Peptides
Electrons
Quantum yield
Cisplatin
Quenching
Ions
Ligands
Catalysts
Water
bis(bipyridyl)ruthenium(II)

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

これを引用

Photoinduced electron transfer in tris(2,2′-bipyridine)ruthenium(ii)- viologen dyads with peptide backbones leading to long-lived charge separation and hydrogen evolution. / Ogawa, Makoto; Balan, Bijitha; Ajayakumar, Gopalakrishnan; Masaoka, Shigeyuki; Kraatz, Heinz Bernhard; Muramatsu, Masayasu; Ito, Syoji; Nagasawa, Yutaka; Miyasaka, Hiroshi; Sakai, Ken.

:: Dalton Transactions, 巻 39, 番号 18, 03.05.2010, p. 4421-4434.

研究成果: ジャーナルへの寄稿記事

Ogawa, Makoto ; Balan, Bijitha ; Ajayakumar, Gopalakrishnan ; Masaoka, Shigeyuki ; Kraatz, Heinz Bernhard ; Muramatsu, Masayasu ; Ito, Syoji ; Nagasawa, Yutaka ; Miyasaka, Hiroshi ; Sakai, Ken. / Photoinduced electron transfer in tris(2,2′-bipyridine)ruthenium(ii)- viologen dyads with peptide backbones leading to long-lived charge separation and hydrogen evolution. :: Dalton Transactions. 2010 ; 巻 39, 番号 18. pp. 4421-4434.
@article{15ffdb2ed0c64e698b2ee0d118e82bac,
title = "Photoinduced electron transfer in tris(2,2′-bipyridine)ruthenium(ii)- viologen dyads with peptide backbones leading to long-lived charge separation and hydrogen evolution",
abstract = "Three 5,5′-disubstituted-2,2′-bipyridine ligands tethered to l-Asp-based peptide backbones having pendant viologen-modified branches, i.e., 5-ethoxycarbonyl-5′-(N-G1-carbamoyl)-2,2′-bipyridine (MV24+), 5,5′-bis(N-G1-carbamoyl)-2,2′- bipyridine (MV48+), and 5,5′-bis(N-G2-carbamoyl)-2, 2′-bipyridine (MV612+), were prepared, where G1 = Asp(NHG3)-NHG3, G2 = Asp(NHG 3)-Asp(NHG3)-NHG3, and G3 = -(CH2)2-+NC5H4-C 5H4N+-CH3, i.e., 2-(1′-methyl-4,4′-bipyridinediium-1-yl)ethyl. These were reacted with cis-Ru(bpy)2Cl2 to give three new dyads [Ru(bpy) 2(MV2)]6+ (RuMV26+), [Ru(bpy) 2(MV4)]10+ (RuMV410+), and [Ru(bpy) 2(MV6)]14+ (RuMV614+), respectively, where bpy = 2,2′-bipyridine. All these dyads undergo extremely efficient intramolecular quenching leading to the formation of charge separated (CS) states (RuIII-MV+), and display a triple exponential decay due to the presence of three classes of conformers with each exhibiting the individual rate of electron transfer. The lifetimes (contributions) were determined as 12.5 ps (94.2{\%}), 791 ps (4.5{\%}), and 18.3 ns (1.2{\%}) for RuMV2, 82.2 ps (79.9{\%}), 1.12 ns (12.4{\%}), and 4.60 ns (7.7{\%}) for RuMV4, and 43.6 ps (71.6{\%}), 593 ps (20.2{\%}), and 3.75 ns (8.1{\%}) for RuMV6. The forward electron transfer rate constants (kET) for the major components were calculated as kET = 8.3 × 1010 s-1 for RuMV2, k ET = 1.2 × 1010 s-1 for RuMV4, and k ET = 2.3 × 1010 s-1 for RuMV6. Further, the lifetimes and quantum yields of charge separated states were determined as τCS = 16 ± 3 ns and ΦCS = 0.81 for RuMV2, τCS = 20 ± 3 ns and ΦCS = 0.92 for RuMV4, and τCS = 20 ± 3 ns and ΦCS = 0.64 for RuMV6. The backward electron transfer rate constants (kBET) were also determined as 6.3 × 107, 5.0 × 107, and 5.0 × 107 s-1 for RuMV2, RuMV4, and RuMV6, respectively. From the analysis of electrical conductivity, the major ion-pair adducts in aqueous media were characterized as RuMV2(PF6)5+ (52{\%}) for RuMV2, RuMV4(PF6)28+ (29{\%}) and RuMV4(PF 6)37+ (32{\%}) for RuMV4, and RuMV6(PF 6)311+ (27{\%}) and RuMV6(PF6) 410+ (29{\%}) for RuMV6, at a total complex concentration of 0.04 mM. The present family is found to be the first example of a Ru(bpy) 32+-MV2+ system in which three orders of magnitude of difference is achieved between the forward and backward electron transfer rate constants. These dyads were finally combined with a Pt(ii)-based H2-evolving catalyst, i.e., cis-diamminedichloroplatinum(ii), to ascertain the applicability of the system towards the visible light-induced water splitting processes.",
author = "Makoto Ogawa and Bijitha Balan and Gopalakrishnan Ajayakumar and Shigeyuki Masaoka and Kraatz, {Heinz Bernhard} and Masayasu Muramatsu and Syoji Ito and Yutaka Nagasawa and Hiroshi Miyasaka and Ken Sakai",
year = "2010",
month = "5",
day = "3",
doi = "10.1039/b922689c",
language = "English",
volume = "39",
pages = "4421--4434",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "18",

}

TY - JOUR

T1 - Photoinduced electron transfer in tris(2,2′-bipyridine)ruthenium(ii)- viologen dyads with peptide backbones leading to long-lived charge separation and hydrogen evolution

AU - Ogawa, Makoto

AU - Balan, Bijitha

AU - Ajayakumar, Gopalakrishnan

AU - Masaoka, Shigeyuki

AU - Kraatz, Heinz Bernhard

AU - Muramatsu, Masayasu

AU - Ito, Syoji

AU - Nagasawa, Yutaka

AU - Miyasaka, Hiroshi

AU - Sakai, Ken

PY - 2010/5/3

Y1 - 2010/5/3

N2 - Three 5,5′-disubstituted-2,2′-bipyridine ligands tethered to l-Asp-based peptide backbones having pendant viologen-modified branches, i.e., 5-ethoxycarbonyl-5′-(N-G1-carbamoyl)-2,2′-bipyridine (MV24+), 5,5′-bis(N-G1-carbamoyl)-2,2′- bipyridine (MV48+), and 5,5′-bis(N-G2-carbamoyl)-2, 2′-bipyridine (MV612+), were prepared, where G1 = Asp(NHG3)-NHG3, G2 = Asp(NHG 3)-Asp(NHG3)-NHG3, and G3 = -(CH2)2-+NC5H4-C 5H4N+-CH3, i.e., 2-(1′-methyl-4,4′-bipyridinediium-1-yl)ethyl. These were reacted with cis-Ru(bpy)2Cl2 to give three new dyads [Ru(bpy) 2(MV2)]6+ (RuMV26+), [Ru(bpy) 2(MV4)]10+ (RuMV410+), and [Ru(bpy) 2(MV6)]14+ (RuMV614+), respectively, where bpy = 2,2′-bipyridine. All these dyads undergo extremely efficient intramolecular quenching leading to the formation of charge separated (CS) states (RuIII-MV+), and display a triple exponential decay due to the presence of three classes of conformers with each exhibiting the individual rate of electron transfer. The lifetimes (contributions) were determined as 12.5 ps (94.2%), 791 ps (4.5%), and 18.3 ns (1.2%) for RuMV2, 82.2 ps (79.9%), 1.12 ns (12.4%), and 4.60 ns (7.7%) for RuMV4, and 43.6 ps (71.6%), 593 ps (20.2%), and 3.75 ns (8.1%) for RuMV6. The forward electron transfer rate constants (kET) for the major components were calculated as kET = 8.3 × 1010 s-1 for RuMV2, k ET = 1.2 × 1010 s-1 for RuMV4, and k ET = 2.3 × 1010 s-1 for RuMV6. Further, the lifetimes and quantum yields of charge separated states were determined as τCS = 16 ± 3 ns and ΦCS = 0.81 for RuMV2, τCS = 20 ± 3 ns and ΦCS = 0.92 for RuMV4, and τCS = 20 ± 3 ns and ΦCS = 0.64 for RuMV6. The backward electron transfer rate constants (kBET) were also determined as 6.3 × 107, 5.0 × 107, and 5.0 × 107 s-1 for RuMV2, RuMV4, and RuMV6, respectively. From the analysis of electrical conductivity, the major ion-pair adducts in aqueous media were characterized as RuMV2(PF6)5+ (52%) for RuMV2, RuMV4(PF6)28+ (29%) and RuMV4(PF 6)37+ (32%) for RuMV4, and RuMV6(PF 6)311+ (27%) and RuMV6(PF6) 410+ (29%) for RuMV6, at a total complex concentration of 0.04 mM. The present family is found to be the first example of a Ru(bpy) 32+-MV2+ system in which three orders of magnitude of difference is achieved between the forward and backward electron transfer rate constants. These dyads were finally combined with a Pt(ii)-based H2-evolving catalyst, i.e., cis-diamminedichloroplatinum(ii), to ascertain the applicability of the system towards the visible light-induced water splitting processes.

AB - Three 5,5′-disubstituted-2,2′-bipyridine ligands tethered to l-Asp-based peptide backbones having pendant viologen-modified branches, i.e., 5-ethoxycarbonyl-5′-(N-G1-carbamoyl)-2,2′-bipyridine (MV24+), 5,5′-bis(N-G1-carbamoyl)-2,2′- bipyridine (MV48+), and 5,5′-bis(N-G2-carbamoyl)-2, 2′-bipyridine (MV612+), were prepared, where G1 = Asp(NHG3)-NHG3, G2 = Asp(NHG 3)-Asp(NHG3)-NHG3, and G3 = -(CH2)2-+NC5H4-C 5H4N+-CH3, i.e., 2-(1′-methyl-4,4′-bipyridinediium-1-yl)ethyl. These were reacted with cis-Ru(bpy)2Cl2 to give three new dyads [Ru(bpy) 2(MV2)]6+ (RuMV26+), [Ru(bpy) 2(MV4)]10+ (RuMV410+), and [Ru(bpy) 2(MV6)]14+ (RuMV614+), respectively, where bpy = 2,2′-bipyridine. All these dyads undergo extremely efficient intramolecular quenching leading to the formation of charge separated (CS) states (RuIII-MV+), and display a triple exponential decay due to the presence of three classes of conformers with each exhibiting the individual rate of electron transfer. The lifetimes (contributions) were determined as 12.5 ps (94.2%), 791 ps (4.5%), and 18.3 ns (1.2%) for RuMV2, 82.2 ps (79.9%), 1.12 ns (12.4%), and 4.60 ns (7.7%) for RuMV4, and 43.6 ps (71.6%), 593 ps (20.2%), and 3.75 ns (8.1%) for RuMV6. The forward electron transfer rate constants (kET) for the major components were calculated as kET = 8.3 × 1010 s-1 for RuMV2, k ET = 1.2 × 1010 s-1 for RuMV4, and k ET = 2.3 × 1010 s-1 for RuMV6. Further, the lifetimes and quantum yields of charge separated states were determined as τCS = 16 ± 3 ns and ΦCS = 0.81 for RuMV2, τCS = 20 ± 3 ns and ΦCS = 0.92 for RuMV4, and τCS = 20 ± 3 ns and ΦCS = 0.64 for RuMV6. The backward electron transfer rate constants (kBET) were also determined as 6.3 × 107, 5.0 × 107, and 5.0 × 107 s-1 for RuMV2, RuMV4, and RuMV6, respectively. From the analysis of electrical conductivity, the major ion-pair adducts in aqueous media were characterized as RuMV2(PF6)5+ (52%) for RuMV2, RuMV4(PF6)28+ (29%) and RuMV4(PF 6)37+ (32%) for RuMV4, and RuMV6(PF 6)311+ (27%) and RuMV6(PF6) 410+ (29%) for RuMV6, at a total complex concentration of 0.04 mM. The present family is found to be the first example of a Ru(bpy) 32+-MV2+ system in which three orders of magnitude of difference is achieved between the forward and backward electron transfer rate constants. These dyads were finally combined with a Pt(ii)-based H2-evolving catalyst, i.e., cis-diamminedichloroplatinum(ii), to ascertain the applicability of the system towards the visible light-induced water splitting processes.

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U2 - 10.1039/b922689c

DO - 10.1039/b922689c

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SN - 1477-9226

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