Department of Chemical Physics, Lund University, Box 124, Lund SE-22100, Sweden.
Centre for Analysis and Synthesis, Department of Chemistry, Lund University, Box 124, Lund SE-22100, Sweden.
Nat Chem. 2015 Nov;7(11):883-9. doi: 10.1038/nchem.2365. Epub 2015 Oct 12.
Solar energy conversion in photovoltaics or photocatalysis involves light harvesting, or sensitization, of a semiconductor or catalyst as a first step. Rare elements are frequently used for this purpose, but they are obviously not ideal for large-scale implementation. Great efforts have been made to replace the widely used ruthenium with more abundant analogues like iron, but without much success due to the very short-lived excited states of the resulting iron complexes. Here, we describe the development of an iron-nitrogen-heterocyclic-carbene sensitizer with an excited-state lifetime that is nearly a thousand-fold longer than that of traditional iron polypyridyl complexes. By the use of electron paramagnetic resonance, transient absorption spectroscopy, transient terahertz spectroscopy and quantum chemical calculations, we show that the iron complex generates photoelectrons in the conduction band of titanium dioxide with a quantum yield of 92% from the (3)MLCT (metal-to-ligand charge transfer) state. These results open up possibilities to develop solar energy-converting materials based on abundant elements.
在光电或光催化中,太阳能的转换包括半导体或催化剂的光捕获或敏化,这是第一步。为此,通常使用稀有元素,但由于所得铁配合物的激发态寿命非常短,它们显然不适用于大规模应用。人们已经做出了巨大的努力来用更丰富的类似物如铁取代广泛使用的钌,但由于所得铁配合物的激发态寿命非常短,因此并没有取得太大的成功。在这里,我们描述了一种铁-氮-杂环卡宾敏化剂的开发,其激发态寿命比传统的铁多吡啶配合物长近千倍。通过使用电子顺磁共振、瞬态吸收光谱、瞬态太赫兹光谱和量子化学计算,我们表明铁配合物从(3)MLCT(金属到配体电荷转移)态以 92%的量子产率在二氧化钛的导带中产生光电子。这些结果为开发基于丰富元素的太阳能转换材料开辟了可能性。