Intramolecular Electronic Coupling Enhances Lateral Electron Transfer across Semiconductor Interfaces
Intramolecular Electronic Coupling Enhances Lateral Electron Transfer across Semiconductor Interfaces
复制标题
分子内电子耦合增强了半导体界面上的横向电子转移
DOI：
10.1021/acs.jpcc.8b04836
复制
发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Meyer, Gerald J.
中科院分区：
文献类型：
--
作者：
Motley, Tyler C.;Meyer, Gerald J.
横向电子转移反应的控制对于许多太阳能转换策略非常重要。在此，四个化合物与两个氧化还原活性基团，一个双（三齿）环化钌金属中心和取代的三苯胺（TPA）的供体分离的有机桥，锚定到TiO 2表面，以促进lateralmolecular间电子转移的研究。一个重要的发现是，TPA+/0的扩散系数约1.6倍大时，桥促进Ru金属中心和TPA之间的分子内电子耦合。在TPA+能够氧化Ru Ⅱ中心或分子内电子耦合较大的条件下，TPA+/0的传递促进了Ru Ⅲ/Ⅱ的电子转移。这些发现表明，氧化还原活性基团之间的协同相互作用可以定制，以控制在分子水平上的电子转移金属氧化物表面。
The control of lateral electron-transfer reactions is important for many solar energy conversion strategies. Herein, four compounds with two redox-active groups, a bis(tridentate) cyclometalated RuIImetal center and a substituted triphenylamine (TPA) donor separated by an organic bridge, were anchored to TiO2surfaces to facilitate study of lateralintermolecular electron transfer. An important finding was that the TPA+/0diffusion coefficients were about 1.6 times larger when the bridge promotedintramolecular electronic coupling between the Ru metal center and TPA. Under conditions where TPA+was able to oxidize the RuIIcenter orintramolecular electronic coupling was large, the RuIII/IIelectron transfer was facilitated by TPA+/0transport. These findings indicate that synergistic interactions between redox-active groups can be tailored to control electron transfer at the molecular level across metal oxide surfaces.