Electronically Regulated Thermally and Light-Gated Electron Transfer from Anions to Naphthalenediimides
Electronically Regulated Thermally and Light-Gated Electron Transfer from Anions to Naphthalenediimides
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DOI：
10.1021/ja2055726
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发表时间：
2011-10-05
影响因子：
15
通讯作者：
Saha, Sourav
中科院分区：
文献类型：
--
作者：
Guha, Samit;Goodson, Flynt S.;Saha, Sourav
通过调节阴离子的刘易斯碱度和NDI的π-酸性，阴离子诱导的电子转移（ET）到π-缺电子萘二酰亚胺（NDI）可以通过两种不同的途径被引导：（1）当阴离子和NDI分别是强电子供体和受体时，将阴离子的HOMO定位在NDI的LUMO之上，打开热阴离子-> NDI ET途径。（2）当弱刘易斯碱性阴离子福尔斯的HOMO低于NDI的LUMO但仍高于其HOMO时，关闭热ET，但是光可以激活前所未有的阴离子->（1）*NDI光诱导的ET途径，从阴离子的HOMO到光生的（1）*NDI的SOMO-1。这两种途径都产生NDI（中心点）自由基阴离子。
Anion-induced electron transfer (ET) to pi-electron-deficient naphthalenediimides (NDIs) can be channeled through two distinct pathways by adjusting the Lewis basicity of the anion and the pi-acidity of the NDI: (1) When the anion and NDI are a strong electron donor and acceptor, respectively, positioning the HOMO of the anion above the LUMO of the NDI, a thermal anion -> NDI ET pathway is turned ON. (2) When the HOMO of a wealdy Lewis basic anion falls below the LUMO of an NDI but still lies above its HOMO, the thermal ET is turned OFF, but light can activate an unprecedented anion -> (1)*NDI photoinduced ET pathway from the anion's HOMO to the photogenerated (1)*NDI's SOMO-1. Both pathways generate NDI(center dot-) radical anions.