Cioffi Carla T, Palkar Amit, Melin Frederic, Kumbhar Amar, Echegoyen Luis, Melle-Franco Manuel, Zerbetto Francesco, Rahman G M Aminur, Ehli Christian, Sgobba Vito, Guldi Dirk M, Prato Maurizio
Center of Excellence on Nanostructured Materials CENMAT, Dipartimento di Scienze Farmaceutiche, Università di Trieste, Piazzale Europa 1, 34127 Trieste, Italy.
Chemistry. 2009;15(17):4419-27. doi: 10.1002/chem.200801818.
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 spectroscopies. 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.
我们描述了一种新型二茂铁 - 碳洋葱衍生物的合成与表征，其中二茂铁作为供电子部分，而碳纳米洋葱（CNO）作为电子受体。通过1,3 - 偶极环加成对CNO进行功能化，所得产物通过透射电子显微镜、热重分析、拉曼光谱和能量色散光谱进行表征。通过电化学和光物理技术研究了Fc - CNO衍生物的电子性质，并辅以量子化学计算。平均而言，CNO呈具有六个壳层的球形外观。功能化使CNO外笼上36个碳原子中的一个碳原子饱和。通过电化学检测到了Fc部分与CNO核心之间的空间相互作用。在低能量和高能量下均观察到荧光，其固有衰减在较低能量下更快。基于理论和实验，我们得出结论，在吸收低能量光子后，具有较大外壳层和较低功能化程度的CNO会产生发射。在高能量下，发射来自具有较小外壳层和较高功能化程度的CNO。
