Electron donor-acceptor interactions in regioselectively synthesized exTTF(2)-C(70)(CF(3))(10) dyads.
Electron donor-acceptor interactions in regioselectively synthesized exTTF(2)-C(70)(CF(3))(10) dyads.
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DOI：
10.1002/chem.200902336
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发表时间：
2010-05
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通讯作者：
Yuta Takano;Yuta Takano;M. Herranz;N. Martín;Gustavo de Miguel Rojas;D. Guldi;I. E. Kareev;S. Strauss;O. Boltalina;T. Tsuchiya;T. Akasaka
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作者：
Yuta Takano;Yuta Takano;M. Herranz;N. Martín;Gustavo de Miguel Rojas;D. Guldi;I. E. Kareev;S. Strauss;O. Boltalina;T. Tsuchiya;T. Akasaka
十(三氟甲基)富勒烯C(1)-C(70)(Cf(3))(10)，其中Cf(3)基团排列在C(6)(Cf(3))(2)边共享六边形的对(7)-偏对位带上，并且现在已经以数百毫克的数量制备，在标准的Bingel-Hirsch条件下与双-PI-扩展的四硫富瓦烯(ExTTF)丙二酸酯衍生物反应，以基于消耗的起始原料以80%的产率得到单一的exTTF(2)-C(70)(Cf(3))(10)区域异构体。通过1D(1)H、(13)C和(19)F核磁共振、2D核磁共振和UV/Vis光谱、基质辅助激光解吸电离(MALDI)和电化学等手段对其进行了表征。ExTTF(2)-C(70)(Cf(3))(10)二元体的循环伏安曲线显示了一个不可逆的二次还原过程，这是典型的逆向Bingel反应，而exTTF的反转电位(E1ox和GT；E2ox)也是常见的现象，导致了单电子、双电子氧化过程。稳态光解和时间分辨光解技术表明，C(1)-C(70)(Cf(3))(10)单重态激发态受到电子转移猝灭的影响。用暂态吸收光谱对生成的电荷分离态进行了鉴定，并测定了甲苯中300ps量级的自由基对寿命。ExTTF(2)-C(70)(Cf(3))(10)二元体代表了利用高可溶性三氟甲基化富勒烯来构建能够模拟光合作用过程的体系的第一个例子，因此在寻找用于光伏应用的新材料方面是有兴趣的。
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.