Departamento de Química Orgánica I, Facultad de Química, Universidad Complutense, 28040 Madrid, Spain.
Chemistry. 2010 May 10;16(18):5343-53. doi: 10.1002/chem.200902336.
The decakis(trifluoromethyl)fullerene C(1)-C(70)(CF(3))(10), in which the CF(3) groups are arranged on a para(7)-meta-para ribbon of C(6)(CF(3))(2) edge-sharing hexagons, and which has now been prepared in quantities of hundreds of milligrams, was reacted under standard Bingel-Hirsch conditions with a bis-pi-extended tetrathiafulvalene (exTTF) malonate derivative to afford a single exTTF(2)-C(70)(CF(3))(10) regioisomer in 80 % yield based on consumed starting material. The highly soluble hybrid was thoroughly characterized by using 1D (1)H, (13)C, and (19)F NMR, 2D NMR, and UV/Vis spectroscopy; matrix-assisted laser desorption ionization (MALDI) mass spectrometry; and electrochemistry. The cyclic voltammogram of the exTTF(2)-C(70)(CF(3))(10) dyad revealed an irreversible second reduction process, which is indicative of a typical retro-Bingel reaction; whereas the usual phenomenon of exTTF inverted potentials (E1ox>E2ox), resulting in a single, two-electron oxidation process, was also observed. Steady-state and time-resolved photolytic techniques demonstrated that the C(1)-C(70)(CF(3))(10) singlet excited state is subject to a rapid electron-transfer quenching. The resulting charge-separated states were identified by transient absorption spectroscopy, and radical pair lifetimes of the order of 300 ps in toluene were determined. The exTTF(2)-C(70)(CF(3))(10) dyad represents the first example of exploitation of the highly soluble trifluoromethylated fullerenes for the construction of systems able to mimic the photosynthetic process, and is therefore of interest in the search for new materials for photovoltaic applications.
现已制备出数百毫克数量级的高纯度[6,6]-二（三氟甲基）富勒烯 C（1）-C（70）（CF（3））（10），它的 CF（3）基团呈对位（7）-间位-对位（ ribbon）排列于 C（6）（CF（3））（2）边缘共享的六边形上。该富勒烯与双-π-扩展四硫富瓦烯（exTTF）丙二酸衍生物在标准 Bingel-Hirsch 条件下反应，以 80%的产率得到单一的 exTTF（2）-C（70）（CF（3））（10）区域异构体，基于消耗的起始原料。该高溶解性的杂化物通过使用 1D（1）H、（13）C 和（19）F NMR、2D NMR 和 UV/Vis 光谱学、基质辅助激光解吸电离（MALDI）质谱和电化学进行了彻底的表征。exTTF（2）-C（70）（CF（3））（10）偶联物的循环伏安图显示出不可逆的第二个还原过程，这表明发生了典型的反-Bingel 反应；而 exTTF 反转电位（E1ox>E2ox）的常见现象，导致单个双电子氧化过程，也被观察到。稳态和时间分辨光解技术表明，C（1）-C（70）（CF（3））（10）单重激发态容易发生快速电子转移猝灭。通过瞬态吸收光谱确定了生成的电荷分离态，并确定了在甲苯中约 300 ps 的自由基对寿命。exTTF（2）-C（70）（CF（3））（10）偶联物代表了利用高溶解性的三氟甲基化富勒烯构建能够模拟光合作用的系统的第一个实例，因此在寻找用于光伏应用的新材料方面具有重要意义。
