Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.
Inorg Chem. 2010 Nov 15;49(22):10223-5. doi: 10.1021/ic1015466. Epub 2010 Oct 15.
The one-electron reduction of triiodide (I(3)(-)) by a reduced ruthenium polypyridyl compound was studied in an acetonitrile solution with the flash-quench technique. Reductive quenching of the metal-to-ligand charge-transfer excited state of Ru(II)(deeb)(3) by iodide generated the reduced ruthenium compound Ru(II)(deeb(-))(deeb)(2) and diiodide (I(2)(•-)). The subsequent reaction of Ru(II)(deeb(-))(deeb)(2) with I(3)(-) indicated that I(2)(•-) was a product that appeared with a second-order rate constant of (5.1 ± 0.2) × 10(9) M(-1) s(-1). After correction for diffusion and some assumptions, Marcus theory predicted a formal potential of -0.58 V (vs SCE) for the one-electron reduction of I(3)(-). The relevance of this reaction to solar energy conversion is discussed.
三碘化物（I(3)(-))的单电子还原是在乙腈溶液中用闪光猝灭技术研究的。Ru(II)(deeb)(3)的金属-配体电荷转移激发态被碘化物还原猝灭，生成还原的钌化合物Ru(II)(deeb(-))(deeb)(2)和二碘化物（I(2)(•-））。Ru(II)(deeb(-))(deeb)(2)与 I(3)(-)的后续反应表明 I(2)(•-)是一种产物，其二级速率常数为（5.1±0.2）×10(9) M(-1) s(-1)。在进行扩散修正和一些假设后，Marcus 理论预测 I(3)(-)单电子还原的形式电位为-0.58 V（相对于 SCE）。讨论了该反应与太阳能转换的相关性。
