Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6 Canada.
J Am Chem Soc. 2012 Feb 22;134(7):3542-8. doi: 10.1021/ja210763n. Epub 2012 Feb 8.
The π-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.
通过 1,4-取代丁二炔的闭环反应合成了π共轭 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、NMR、电化学、X 射线晶体学和密度泛函理论 (DFT) 计算研究了 Br2 对碲吩化合物 1 和 3 的加成反应。当 Br2 加到碲原子中心时，吸收光谱向低能量移动。从电化学和 DFT 计算我们可以看出，这是由于最低未占据轨道的降低引起的。最高占据轨道也降低了，但程度较小。这种吸收光谱的移动和氧化电位的降低可以为修饰含碲材料提供一种方法。两电子加成反应有望催化储能反应。
