Tellurophenes with Delocalized π-Systems and Their Extended Valence Adducts
Tellurophenes with Delocalized π-Systems and Their Extended Valence Adducts
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DOI：
10.1021/ja210763n
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发表时间：
2012-02-22
影响因子：
15
通讯作者：
Seferos, Dwight S.
中科院分区：
文献类型：
--
作者：
McCormick, Theresa M.;Jahnke, Ashlee A.;Seferos, Dwight S.
通过1，4-取代丁二炔的关环反应，合成了π共轭的2，5-取代碲吩化合物2，5-双（2-（9，9-二己基芴））碲吩（1）和2，5-二苯基碲吩（3）。通过吸收光谱、核磁共振、电化学、X射线晶体学和密度泛函理论（DFT）计算研究了碲吩化合物1和3与Br-2的氧化加成反应。当Br-2加入到碲中心时，吸收光谱向较低的能量移动。从电化学和DFT计算，我们表明，这是由于降低最低未占轨道。最高占据轨道也被降低，但程度较小。吸收光谱的这种偏移和氧化电位的降低可以提供一种对含碲吩的材料进行改性的方法。双电子氧化加成反应在催化储能反应中具有广阔的应用前景。
The pi-conjugated 2,5-substituted tellurophene compounds 2,5-bis(2-(9,9-dihexylfluorene))tellurophene (1) and 2,5-diphenyltellurophene (3) were synthesized through ring closing reactions of 1,4-substituted butadiyne. The oxidative addition of Br-2 to tellurophene compounds 1 and 3 was studied through absorption spectroscopy, NMR, electrochemistry, X-ray crystallography, and density functional theory (DFT) calculations. When Br-2 adds to the tellurium center the absorption spectrum shifts to a lower energy. From electrochemistry and DFT calculations we show that this is caused by lowering the lowest unoccupied orbital. The highest occupied orbital is also lowered, but to a lesser extent. This shift in absorption spectrum and lowering of the oxidation potential can provide a method to modify tellurophene containing materials. The two-electron oxidative addition is promising for catalyzing energy storage reactions.