Vinyl spacers-tuning electron transfer through fluorene-based molecular wires
Vinyl spacers-tuning electron transfer through fluorene-based molecular wires
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DOI：
10.1039/c0ee00499e
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发表时间：
2011-03-01
影响因子：
32.5
通讯作者：
Martin, Nazario
中科院分区：
文献类型：
--
作者：
Wielopolski, Mateusz;Santos, Jose;Martin, Nazario
已经使用低聚乙烯基芴（oFV）接头连接电活性实体来合成了结合作为电子供体的联合收割机pi-延伸的四硫富瓦烯（exTTF）和作为电子受体的C-60的刚性和可溶性电子供体-受体缀合物（3和11）。荧光和瞬态吸收测量证实，光致激发诱导的电荷转移反应在28埃的距离在THF中。实验和理论都表明，在低聚芴分子线中引入亚乙烯基间隔基可以显著改善电荷转移特性，得到0.075 +/-0.001埃（-1）的β值。更高的轨道重叠引起的π共轭增强是这种趋势的原因。
Rigid and soluble electron donor-acceptor conjugates (3 and 11) that combine pi-extended tetrathiafulvalene (exTTF) as an electron donor and C-60 as an electron acceptor have been synthesized using oligo-vinylfluorene (oFV) linkers to connect the electroactive entities. Fluorescence and transient absorption measurements confirm that light-induced excitation induces charge-transfer reactions over distances of 28 angstrom in THF. The incorporation of vinylene spacers into oligofluorene molecular wires has been shown both experimentally and theoretically to improve the charge-transfer features significantly to give a beta value of 0.075 +/- 0.001 angstrom(-1). Enhanced pi-conjugation caused by higher orbital overlap is responsible for this trend.