Binding of Scandium Ions to Metalloporphyrin-Flavin Complexes for Long-Lived Charge Separation

Takahiko Kojima, Ryosuke Kobayashi, Tomoya Ishizuka, Shinya Yamakawa, Hiroaki Kotani, Tatsuaki Nakanishi, Kei Ohkubo, Yoshihito Shiota, Kazunari Yoshizawa, Shunichi Fukuzumi

研究成果: ジャーナルへの寄稿記事

6 引用 (Scopus)

抄録

A porphyrin-flavin-linked dyad and its zinc and palladium complexes (MPor-Fl: 2-M, M=2 H, Zn, and Pd) were newly synthesized and the X-ray crystal structure of 2-Pd was determined. The photodynamics of 2-M were examined by femto- and nanosecond laser flash photolysis measurements. Photoinduced electron transfer (ET) in 2-H2 occurred from the singlet excited state of the porphyrin moiety (H2Por) to the flavin (Fl) moiety to produce the singlet charge-separated (CS) state 1(H2Por.+-Fl.-), which decayed through back ET (BET) to form 3[H2Por]∗-Fl with rate constants of 1.2×1010 and 1.2×109 s-1, respectively. Similarly, photoinduced ET in 2-Pd afforded the singlet CS state, which decayed through BET to form 3[PdPor]∗-Fl with rate constants of 2.1×1011 and 6.0×1010 s-1, respectively. The rate constant of photoinduced ET and BET of 2-M were related to the ET and BET driving forces by using the Marcus theory of ET. One and two Sc3+ ions bind to the flavin moiety to form the Fl-Sc3+ and Fl-(Sc3+)2 complexes with binding constants of K 1=2.2×105 M -1 and K 2=1.8×103 M -1, respectively. Other metal ions, such as Y3+, Zn2+, and Mg2+, form only 1:1 complexes with flavin. In contrast to 2-M and the 1:1 complexes with metal ions, which afforded the short-lived singlet CS state, photoinduced ET in 2-Pd Sc3+ complexes afforded the triplet CS state (3[PdPor.+-Fl.--(Sc3+)2]), which exhibited a remarkably long lifetime of τ=110 ms (k BET=9.1 s-1). More than transient: A porphyrin-flavin-linked dyad and its zinc and palladium complexes were synthesized and the X-ray crystal structure of the palladium complex was determined. The Pd-Sc3+ complex afforded a remarkably long lifetime of 110 ms of the charge-separated state (see figure).

元の言語英語
ページ(範囲)15518-15532
ページ数15
ジャーナルChemistry - A European Journal
20
発行部数47
DOI
出版物ステータス出版済み - 11 1 2014

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Scandium
Metalloporphyrins
Ions
Electrons
Porphyrins
Palladium
Rate constants
Metal ions
Zinc
Crystal structure
X rays
Photolysis
Excited states
Electron energy levels
4,6-dinitro-o-cresol
Lasers

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

これを引用

Kojima, T., Kobayashi, R., Ishizuka, T., Yamakawa, S., Kotani, H., Nakanishi, T., ... Fukuzumi, S. (2014). Binding of Scandium Ions to Metalloporphyrin-Flavin Complexes for Long-Lived Charge Separation. Chemistry - A European Journal, 20(47), 15518-15532. https://doi.org/10.1002/chem.201403960

Binding of Scandium Ions to Metalloporphyrin-Flavin Complexes for Long-Lived Charge Separation. / Kojima, Takahiko; Kobayashi, Ryosuke; Ishizuka, Tomoya; Yamakawa, Shinya; Kotani, Hiroaki; Nakanishi, Tatsuaki; Ohkubo, Kei; Shiota, Yoshihito; Yoshizawa, Kazunari; Fukuzumi, Shunichi.

:: Chemistry - A European Journal, 巻 20, 番号 47, 01.11.2014, p. 15518-15532.

研究成果: ジャーナルへの寄稿記事

Kojima, T, Kobayashi, R, Ishizuka, T, Yamakawa, S, Kotani, H, Nakanishi, T, Ohkubo, K, Shiota, Y, Yoshizawa, K & Fukuzumi, S 2014, 'Binding of Scandium Ions to Metalloporphyrin-Flavin Complexes for Long-Lived Charge Separation', Chemistry - A European Journal, 巻. 20, 番号 47, pp. 15518-15532. https://doi.org/10.1002/chem.201403960
Kojima T, Kobayashi R, Ishizuka T, Yamakawa S, Kotani H, Nakanishi T その他. Binding of Scandium Ions to Metalloporphyrin-Flavin Complexes for Long-Lived Charge Separation. Chemistry - A European Journal. 2014 11 1;20(47):15518-15532. https://doi.org/10.1002/chem.201403960
Kojima, Takahiko ; Kobayashi, Ryosuke ; Ishizuka, Tomoya ; Yamakawa, Shinya ; Kotani, Hiroaki ; Nakanishi, Tatsuaki ; Ohkubo, Kei ; Shiota, Yoshihito ; Yoshizawa, Kazunari ; Fukuzumi, Shunichi. / Binding of Scandium Ions to Metalloporphyrin-Flavin Complexes for Long-Lived Charge Separation. :: Chemistry - A European Journal. 2014 ; 巻 20, 番号 47. pp. 15518-15532.
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abstract = "A porphyrin-flavin-linked dyad and its zinc and palladium complexes (MPor-Fl: 2-M, M=2 H, Zn, and Pd) were newly synthesized and the X-ray crystal structure of 2-Pd was determined. The photodynamics of 2-M were examined by femto- and nanosecond laser flash photolysis measurements. Photoinduced electron transfer (ET) in 2-H2 occurred from the singlet excited state of the porphyrin moiety (H2Por) to the flavin (Fl) moiety to produce the singlet charge-separated (CS) state 1(H2Por.+-Fl.-), which decayed through back ET (BET) to form 3[H2Por]∗-Fl with rate constants of 1.2×1010 and 1.2×109 s-1, respectively. Similarly, photoinduced ET in 2-Pd afforded the singlet CS state, which decayed through BET to form 3[PdPor]∗-Fl with rate constants of 2.1×1011 and 6.0×1010 s-1, respectively. The rate constant of photoinduced ET and BET of 2-M were related to the ET and BET driving forces by using the Marcus theory of ET. One and two Sc3+ ions bind to the flavin moiety to form the Fl-Sc3+ and Fl-(Sc3+)2 complexes with binding constants of K 1=2.2×105 M -1 and K 2=1.8×103 M -1, respectively. Other metal ions, such as Y3+, Zn2+, and Mg2+, form only 1:1 complexes with flavin. In contrast to 2-M and the 1:1 complexes with metal ions, which afforded the short-lived singlet CS state, photoinduced ET in 2-Pd Sc3+ complexes afforded the triplet CS state (3[PdPor.+-Fl.--(Sc3+)2]), which exhibited a remarkably long lifetime of τ=110 ms (k BET=9.1 s-1). More than transient: A porphyrin-flavin-linked dyad and its zinc and palladium complexes were synthesized and the X-ray crystal structure of the palladium complex was determined. The Pd-Sc3+ complex afforded a remarkably long lifetime of 110 ms of the charge-separated state (see figure).",
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AU - Kojima, Takahiko

AU - Kobayashi, Ryosuke

AU - Ishizuka, Tomoya

AU - Yamakawa, Shinya

AU - Kotani, Hiroaki

AU - Nakanishi, Tatsuaki

AU - Ohkubo, Kei

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Fukuzumi, Shunichi

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N2 - A porphyrin-flavin-linked dyad and its zinc and palladium complexes (MPor-Fl: 2-M, M=2 H, Zn, and Pd) were newly synthesized and the X-ray crystal structure of 2-Pd was determined. The photodynamics of 2-M were examined by femto- and nanosecond laser flash photolysis measurements. Photoinduced electron transfer (ET) in 2-H2 occurred from the singlet excited state of the porphyrin moiety (H2Por) to the flavin (Fl) moiety to produce the singlet charge-separated (CS) state 1(H2Por.+-Fl.-), which decayed through back ET (BET) to form 3[H2Por]∗-Fl with rate constants of 1.2×1010 and 1.2×109 s-1, respectively. Similarly, photoinduced ET in 2-Pd afforded the singlet CS state, which decayed through BET to form 3[PdPor]∗-Fl with rate constants of 2.1×1011 and 6.0×1010 s-1, respectively. The rate constant of photoinduced ET and BET of 2-M were related to the ET and BET driving forces by using the Marcus theory of ET. One and two Sc3+ ions bind to the flavin moiety to form the Fl-Sc3+ and Fl-(Sc3+)2 complexes with binding constants of K 1=2.2×105 M -1 and K 2=1.8×103 M -1, respectively. Other metal ions, such as Y3+, Zn2+, and Mg2+, form only 1:1 complexes with flavin. In contrast to 2-M and the 1:1 complexes with metal ions, which afforded the short-lived singlet CS state, photoinduced ET in 2-Pd Sc3+ complexes afforded the triplet CS state (3[PdPor.+-Fl.--(Sc3+)2]), which exhibited a remarkably long lifetime of τ=110 ms (k BET=9.1 s-1). More than transient: A porphyrin-flavin-linked dyad and its zinc and palladium complexes were synthesized and the X-ray crystal structure of the palladium complex was determined. The Pd-Sc3+ complex afforded a remarkably long lifetime of 110 ms of the charge-separated state (see figure).

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