当前位置：
X-MOL 学术
›
J. Phys. Chem. A
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Chemical Scavenging Yields for Short-Lived Products from the Visible Light Photoionization of the Tris(bipyridine)ruthenium(II) Triplet Metal-to-Ligand Charge-Transfer Excited State
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-11-02 00:00:00 , DOI: 10.1021/acs.jpca.8b08471 Marim K. Alnaed 1 , John F. Endicott 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-11-02 00:00:00 , DOI: 10.1021/acs.jpca.8b08471 Marim K. Alnaed 1 , John F. Endicott 1
Affiliation
|
The rate of visible light photoionization of the tris(bipyridine)ruthenium(II) triplet metal-to-ligand charge-transfer excited state (3MLCT) is very strongly dependent on the acid concentration in aqueous solution, and the pattern of this dependence is similar to that reported for the photoionization of iodide. With 405 nm visible irradiation of 3MLCT, less than 15% of the photoionized products appear as free solvated electrons in bulk solution, while more than 75% of the photoproducts appear to be solvent-separated, (oxidized substrate)–electron ion pairs that efficiently recombine with the photo-oxidized complex in the absence of an electron scavenger. The quantum yield of free solvated electrons generated by these 405 nm irradiations is approximately 0.004, but the net quantum yield of scavengeable electrons is estimated to be about 0.04. A visible-region photoionization threshold energy for the 3MLCT is consistent with thermodynamic expectations, and similar behavior is expected for many redox-active complexes.
中文翻译：
三（联吡啶）钌（II）三重态金属-配体电荷转移激发态可见光光电离的短命产品化学清除率
三（联吡啶）钌（II）三重态金属与配体的电荷转移激发态（3 MLCT）的可见光光电离速率非常强地取决于水溶液中的酸浓度，这种依赖性的模式是与报道的碘离子光电离相似。用405 nm的可见光照射3MLCT中，只有不到15％的光电离产物以散装溶液形式显示为游离的溶剂化电子，而超过75％的光电离产物似乎是溶剂分离的（被氧化的底物）-电子离子对，可与光氧化有效地重组在没有电子清除剂的情况下是复杂的。由这些405 nm辐照产生的自由溶剂化电子的量子产率约为0.004，但可清除电子的净量子产率估计约为0.04。3 MLCT的可见光区电离阈值能量与热力学预期一致，并且对于许多氧化还原活性复合物，预期具有相似的行为。
更新日期：2018-11-02
中文翻译：
三（联吡啶）钌（II）三重态金属-配体电荷转移激发态可见光光电离的短命产品化学清除率
三（联吡啶）钌（II）三重态金属与配体的电荷转移激发态（3 MLCT）的可见光光电离速率非常强地取决于水溶液中的酸浓度，这种依赖性的模式是与报道的碘离子光电离相似。用405 nm的可见光照射3MLCT中，只有不到15％的光电离产物以散装溶液形式显示为游离的溶剂化电子，而超过75％的光电离产物似乎是溶剂分离的（被氧化的底物）-电子离子对，可与光氧化有效地重组在没有电子清除剂的情况下是复杂的。由这些405 nm辐照产生的自由溶剂化电子的量子产率约为0.004，但可清除电子的净量子产率估计约为0.04。3 MLCT的可见光区电离阈值能量与热力学预期一致，并且对于许多氧化还原活性复合物，预期具有相似的行为。
京公网安备 11010802027423号