Anionic Fluorinated Zn-porphyrin Combined with Cationic Endohedral Li-fullerene for Long-Lived Photoinduced Charge Separation with Low Energy Loss

Kazuhira Miwa, Shinobu Aoyagi, Takahiro Sasamori, Hiroshi Ueno, Hiroshi Okada, Kei Ohkubo

研究成果: Article査読

抄録

Here we report an anionic meso-tetrakis(4-carboxymethylthio-2,3,5,6-tetrafluorophenyl) zinc porphyrin (ZnTF4PPTC4-) to form a supramolecular complex with a cationic lithium endohedral [60]fullerene (Li+@C60). The supramolecular ZnTF4PPTC4-/Li+@C60 complex formed by strong electrostatic attraction with a large binding constant generates a long-lived charge-separated (CS) state with low energy loss by photoinduced electron transfer from ZnTF4PPTC4- to Li+@C60. The anionic fluorinated zinc porphyrin with high oxidation potential reduces the energy loss associated with the charge separation and enhances the energy level of the CS state. The energy level of the CS state determined by electrochemical measurements is at 0.94 eV, which is much higher than that of a similar supramolecular complex using an anionic meso-tetrakis(sulfonatophenyl) zinc porphyrin (ZnTPPS4-) at 0.55 eV. Time-resolved transient absorption spectroscopy demonstrates that ZnTF4PPTC4-/Li+@C60 generates a long-lived CS state with a lifetime of 0.29 ms in a binary solvent of acetonitrile and chlorobenzene. The lifetime of the CS state is comparable to that of ZnTPPS4-/Li+@C60 in benzonitrile.

本文言語English
ページ(範囲)918-925
ページ数8
ジャーナルJournal of Physical Chemistry B
125
3
DOI
出版ステータスPublished - 2021 1 28

ASJC Scopus subject areas

  • 物理化学および理論化学
  • 表面、皮膜および薄膜
  • 材料化学

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