title: Ferrocene-functionalized carbon nanoparticles.
abstract: Carbon nanoparticles were synthesized from natural gas soot and functionalized with ferrocenyl moieties by using 4-ferrocenylphenyldiazonium as the reactive precursor. The incorporation of the ferrocenyl units onto the carbon nanoparticle surface was confirmed by varied spectroscopic measurements. For instance, in FTIR measurements the characteristic vibrational bands of the ferrocenyl and phenyl moieties could be clearly identified. XPS measurements showed that there were approximately 31.9 ferrocenyl units per nanoparticle. UV-vis spectroscopic measurements displayed an absorption band at ca. 465 nm which was consistent with the optical characteristics of ferrocenyl derivatives. Furthermore, with surface functionalization by the ferrocenyl moieties, the photoluminescence of the carbon nanoparticles was found to diminish in intensity and red-shift in energy with the addition of NOBF(4). This was accounted for by the formation of varied electron-accepting moieties on the particle surface, such as positively charged ferrocenium, quinone-like derivatives, and nitrosation of the aromatic rings of the graphitic cores. Interestingly, in electrochemical studies the nanoparticle-bound ferrocenyl moieties were found to exhibit two pairs of voltammetric waves with a difference of their formal potentials at about 78 mV, suggesting nanoparticle-mediated intraparticle charge delocalization at mixed valence as a result of the strong core-ligand covalent bonds and the conductive sp(2) carbon matrix of the graphitic cores. Consistent behaviors were observed in near-infrared measurements, indicating that the particles behaved analogously to a Class I/II mixed-valence compound.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, California 95064, USA.
authors.forename: Yang
authors.initials: Y
authors.lastname: Song
authors.forename: Xiongwu
authors.initials: X
authors.lastname: Kang
authors.forename: Nathaniel B
authors.initials: NB
authors.lastname: Zuckerman
authors.forename: Bruce
authors.initials: B
authors.lastname: Phebus
authors.forename: Joseph P
authors.initials: JP
authors.lastname: Konopelski
authors.forename: Shaowei
authors.initials: S
authors.lastname: Chen
mesh_terms: D005296:Ferrous Compounds / Q000737:chemistry*; D008163:Luminescent Measurements / Q000379:methods*; D008422:Materials Testing; D000075163:Metallocenes; D053758:Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure*; D010316:Particle Size; D013499:Surface Properties
chemical_list: D005296:Ferrous Compounds; D000075163:Metallocenes; C004998:ferrocene