Ultrafast Photoinduced Electron Transfer from Peroxide Dianion

被引：13

作者：

Anderson, Bryce L. ^{[1
]}

Maher, Andrew G. ^{[1
,2
]}

Nava, Matthew ^{[2
]}

Lopez, Nazario ^{[2
]}

Cummins, Christopher C. ^{[2
]}

Nocera, Daniel G. ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

[2] MIT, Dept Chem, Cambridge, MA 02139 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2015年 / 119卷 / 24期

基金：

美国国家科学基金会;

关键词：

EXCITED-STATE; CHARGE-TRANSFER; BASIS-SETS; COMPLEXES; ENERGY; REDUCTION; EMISSION; RUTHENIUM(II); DYNAMICS; LITHIUM;

D O I：

10.1021/jp5110505

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The encapsulation of peroxide dianion by hexacarboxamide cryptand provides a platform for the study of electron transfer of isolated peroxide anion. Photoinitiated electron transfer (ET) between freely diffusing Ru(bpy)(3)(2+) and the peroxide dianion occurs with a rate constant of 2.0 x 10(10) M-1 s(-1). A competing electron transfer quenching pathway is observed within an ion pair. Picosecond transient spectroscopy furnishes a rate constant of 1.1 x 10(10) s(-1) for this first-order process. A driving force dependence for the ET rate within the ion pair using a series of Ru(bpy)(3)(2+) derivatives allows for the electronic coupling and reorganization energies to be assessed. The ET reaction is nonadiabatic and dominated by a large inner-sphere reorganization energy, in accordance with that expected for the change in bond distance accompanying the conversion of peroxide dianion to superoxide anion.

引用

页码：7422 / 7429

页数：8