Organic-inorganic azafullerene-gold c59n-au nanohybrid: synthesis, characterization, and properties
Organic-inorganic azafullerene-gold c59n-au nanohybrid: synthesis, characterization, and properties
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有机-无机氮杂富勒烯-金 c59n-au 纳米杂化物：合成、表征和性能
DOI：
10.1002/chem.201403517
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发表时间：
2014
影响因子：
4.3
通讯作者：
and N. Tagmatarchis
中科院分区：
文献类型：
--
作者：
G. Rotas;M. Niemi;N.V. Tkachenko;S. Zhao;H. Shinohara;and N. Tagmatarchis
氮杂富勒烯（C59 N）使用曼尼希型反应官能化，然后随后与硫辛酸缩合以产生二硫戊环改性的C59 N。在接下来的步骤中，来自C59 N核的延伸的二硫戊环部分用于用金纳米颗粒（Au NP）装饰氮杂富勒烯球。后者最初用十二硫醇（DT双Au）稳定，然后通过与二硫戊环官能化的C59 N的配体交换反应整合在氮杂富勒烯上，以产生C59 N/DT双Au纳米杂化物。通过光谱学和显微镜对纳米混合物进行了充分表征，揭示了直径在2-5 nm范围内的球形纳米颗粒的形成，如通过HR-TEM成像的。 在C59 N/DT-Au纳米杂化材料的电子吸收光谱中，观察到了Au纳米颗粒的特征表面等离子体带，但与DT-Au纳米颗粒相比，该表面等离子体带发生了红移。SPB的红移指示在C59 N/DT双金属Au纳米杂化物中，根据如通过TEM观察到的聚集的NP的形成，Au NP的更紧密的粒子间接近。C59 N/DT双金属Au的激发态相互作用通过光致发光分析来探测。发现C59 N在819 nm处的弱发射在C59 N/DT双金属Au中蓝移了14 nm，但强度更强，因此表明在有机-无机C59 N/DT双金属Au纳米杂化物内能量转移到C59 N。 最后，借助于泵浦-探测测量和瞬态吸收光谱，确定了C59 N单重激发态的形成。
Azafullerene (C59N) was functionalized using a Mannich‐type reaction and then subsequently condensed with lipoic acid to yield dithiolane‐modified C59N. In the following step, the extended dithiolane moiety from the C59N core was utilized to decorate the azafullerene sphere with gold nanoparticles (Au NPs). The latter were initially stabilized with dodecanothiol (DT⋅Au) and then integrated on azafullerene through a ligand exchange reaction with the dithiolane‐functionalized C59N to produce the C59N/DT⋅Au nanohybrid. The nanohybrid was fully characterized by spectroscopy and microscopy, revealing the formation of spherical nanoparticles with a diameter in the range of 2–5 nm, as imaged by HR‐TEM. In the electronic absorption spectrum of C59N/DT⋅Au nanohybrid, the characteristic surface plasmon band (SPB) of Au NPs was observed, however, it was redshifted compared with that of DT⋅Au. The redshift of the SPB is indicative of closer interparticle proximity of Au NPs, in accordance with the formation of aggregated NPs as observed by TEM, in C59N/DT⋅Au nanohybrid. Excited‐state interactions in C59N/DT⋅Au were probed by photoluminescence assays. It was found that the weak emission of C59N at 819 nm was blueshifted by 14 nm in C59N/DT⋅Au, but was stronger in intensity, thus suggesting energy transfer to C59N, within the organic–inorganic C59N/DT⋅Au nanohybrid. Finally, with the aid of pump–probe measurements and transient absorption spectroscopy, the formation of the singlet excited state of C59N was identified.