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Electron photodetachment from iodide in ionic liquids through charge-transfer-to-solvent band excitation

CTTSバンド励起によるイオン液体中のヨウ化物からの電子光脱理

加藤 隆二*; 吉田 陽一*; 勝村 庸介; 高橋 憲司*

Kato, Ryuji*; Yoshida, Yoichi*; Katsumura, Yosuke; Takahashi, Kenji*

Solvation of iodide and electrons in an ionic liquid (${it N,N,N}$-trimethyl-$$n$$-propylammonium bis(trifluoromethanesulfonyl) imide; TMPA-TFSI) was studied through the absorption spectra of the charge-transfer-to-solvent(CTTS) state of iodide and of solvated electrons. The interaction between the TMPA cation and iodide was strong, where as electrons were weakly solvated in TMPA-TFSI. We followed electron photodetachment from iodide to the ionic liquid and formation of the solvated electrons by observing absorption in the visible and near-infrared regions using a nanosecond laser flash photolysis method. The quantum yield of the photodetachment in TMPA-TFSI was estimated to be 0.34, which is much higher than that in a high-concentration aqueous salt solution previously reported. We also examined a reaction of the solvated electrons with the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (Bmim-TFSI) as a solute in TMPA-TFSI. The reaction rate was determined to be 5.3$$times$$10$$^{8}$$ M$$^{-1}$$s$$^{-1}$$. The electrons before full solvation (dry electrons) reacted with Bmim cations efficiently. These observations suggest that the electrons in TMPA-TFSI can move easily before solvation.

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パーセンタイル:76.58

分野:Chemistry, Physical

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