A Carbon Nano-Onion-Ferrocene Donor-Acceptor System: Synthesis, Characterization and Properties
A Carbon Nano-Onion-Ferrocene Donor-Acceptor System: Synthesis, Characterization and Properties
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DOI：
10.1002/chem.200801818
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发表时间：
2009-01-01
影响因子：
4.3
通讯作者：
Prato, Maurizio
中科院分区：
文献类型：
--
作者：
Cioffi, Carla T.;Palkar, Amit;Prato, Maurizio
我们描述了一种新型二茂铁-碳洋葱衍生物的合成和表征，其中二茂铁作为电子给体，而碳纳米洋葱（CNO）作为电子受体。采用1,3偶极环加成方法对化合物进行了官能化，并利用透射电子显微镜、热重分析、拉曼光谱和能量色散光谱对产物进行了表征。利用电化学和光物理技术，并辅以量子化学计算，研究了Fc-CNO衍生物的电子性质。平均而言，CNOs有一个球形的外观，有六个壳。官能化使CNO外笼上36个碳原子中的一个碳原子饱和。通过电化学方法检测了Fc片段与CNO核心之间的空间相互作用。在低能量和高能量下观察到荧光，其内在衰减在低能量下更快。基于理论和实验，我们得出结论，在低能量光子吸收后，CNOs有更大的外壳和更低的官能化程度的发射。在高能量时，辐射来自具有更小外壳和更高功能化程度的CNOs。
We describe the synthesis and characterization of a novel ferrocene-carbon onion derivative, where ferrocene acts as an electron-donating moiety, while the carbon nano-onion (CNO) serves as the electron acceptor. CNOs were functionalized by 1,3-dipolar cycloaddition and the resulting products were characterized by transmission electron microscopy, thermogravimetric analysis, Raman and energy dispersive spectroscopics. The electronic properties of the Fc-CNO derivative were investigated by electrochemical and photophysical techniques, complemented by quantum chemical calculations. On average, the CNOs have a spherical appearance with six shells. Functionalization saturates one carbon atom in 36 carbon atoms on the outer cage of the CNO. Through-space interactions between the Fc moiety and the CNO core were detected electrochemically. Fluorescence was observed at low and high energies with an intrinsic decay that is faster at lower energies. Based on theory and experiment, we conclude that, after absorption of a photon at low energy, there is emission from CNOs characterized by larger external shells and a lower degree of functionalization. At high energy, emission comes from CNOs with smaller external shells and a higher degree of functionalization.