Organic–Inorganic Azafullerene‐Gold C59N‐Au Nanohybrid: Synthesis, Characterization, and Properties. Issue 45 (15th September 2014)

• Record Type: Journal Article
• Authors: Rotas, Georgios; Niemi, Marja; Tkachenko, Nikolai V.; Zhao, Sihan; Shinohara, Hisanori; Tagmatarchis, Nikos
• Is Part Of: Chemistry. Volume 20:Issue 45(2014)
• Page Start: 14729
• Page End: 14735
• Publication Date: 2014-09-15
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201403517
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Azafullerene (C<sub>59</sub>N) was functionalized using a Mannich‐type reaction and then subsequently condensed with lipoic acid to yield dithiolane‐modified C<sub>59</sub>N. In the following step, the extended dithiolane moiety from the C<sub>59</sub>N core was utilized to decorate the azafullerene sphere with gold nanoparticles (Au NPs). The latter were initially stabilized with dodecanothiol (DT<bold>⋅</bold>Au) and then integrated on azafullerene through a ligand exchange reaction with the dithiolane‐functionalized C<sub>59</sub>N to produce the C<sub>59</sub>N/DT<bold>⋅</bold>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 C<sub>59</sub>N/DT<bold>⋅</bold>Au nanohybrid, the characteristic surface plasmon band (SPB) of Au NPs was observed, however, it was redshifted compared with that of DT<bold>⋅</bold>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 C<sub>59</sub>N/DT<bold>⋅</bold>Au nanohybrid. Excited‐state interactions in C<sub>59</sub>N/DT<bold>⋅</bold>Au were probed by photoluminescence assays. It was found that the weak emission of C<sub>59</sub>N at 819 nm was blueshifted by 14 nm in C<sub>59</sub>N/DT<bold>⋅</bold>Au, but was stronger in intensity, thus suggesting energy transfer to C<sub>59</sub>N, within the organic–inorganic C<sub>59</sub>N/DT<bold>⋅</bold>Au nanohybrid. Finally, with the aid of pump–probe measurements and transient absorption spectroscopy, the formation of the singlet excited state of C<sub>59</sub>N was identified.</p> </abstract>