Electrochemical properties of soluble fullerene derivatives (original) (raw)
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Synthesis and electrochemical properties of ionic fullerene derivatives
Carbon, 2000
1,3-Dipolar cycloaddition of azomethine ylides to C generates a family of fullerene derivatives, colloquially termed 60 fulleropyrrolidines. In this paper, we report the synthesis and the electrochemical properties of fulleropyrrolidine and fulleropyrrolidinium ion derivatives. Cyclic voltammetry measurements, performed using ultramicroelectrodes at 2608C with scan rates as high as 50 V/ s, allowed, for the first time in fullerene derivatives, the observation of six fullerene-centered reductions. These derivatives also exhibit enhanced electron-accepting properties with respect to both the parent fulleropyrrolidine derivatives and C . Bulk electrolysis carried out at the stage of the first reduction potential, gives rise to a 60 stable zwitterion, with both anion and cation located on the fullerene derivatives.
A large series of disubstituted fulleropyrrolidines was synthesized and analyzed by cyclic voltammetry. The three main groups of target compounds differ by a flexible N-chain, while their further diversity was achieved by the introduction of various rigid, aryl substituents at the pyrrolidine carbon. Some dialkyl analogues were also designed for comparison, A standard [3+2]cycloaddition of in situ generated azomethine ylides to C 60 afforded a variety of disubstituted fulleropyrrolidines. Furthermore, a set of dumbbell-shaped di(fulleropyrrolidine) derivatives containing rigid fumaryl or isophthaloyl diamide platform was prepared with the aim of investigating a long-range effect of the second fulleropyrrolidine moiety on their electrochemical properties. All compounds were fully characterized by comparative analysis of spectral data, while examination of electrochemical properties was performed on representative samples, distinguished by main structural subunits. All compounds expressed quite similar electron-accepting ability, lower than C 60 , but higher in comparison to structurally similar N-methylfulleropyrrolidine.
International Journal of Photoenergy, 2001
A fullerene derivative in which two oligophenylenevinylene (OPV) groups are attached to C 60 through a pyrrolidine ring has been prepared and photophysical studies in CH 2 Cl 2 solution show that photoinduced energy transfer from the OPV moieties to C 60 occurs, and not electron transfer. On passing to a more polar solvent such as benzonitrile, again no evidence of electron transfer is found. the expected signals. Interestingly, the signals corresponding to some of the protons of the pyrrolidine ring and those of the phenyl group directly attached to it Vol. 3
Structural and electronic properties of pyrrolidine-functionalized [60] fullerenes
We have investigated energetic, geometric, electronic, and field emission properties of three recently synthesized fulleropyrrolidines based on the density functional theory method B3LYP/6-31G(d). Fulleropyrrolidines show higher conductivity, and solubility in water, and smaller work function in comparison with the pristine C 60 fullerene. The functionalization of C 60 with different pyrrolidines containing -NH 2 , NO, or NO 2 groups transforms it to an n-type semiconductor. The functionalization can also dramatically enhance the electrophilicity of the C 60 about 23-37%. Moreover, it should be mentioned that the work function is mainly influenced by the pyrrolidine containing -NO 2 group whereas the conductivity is largely affected by the one containing -NH 2 functionality.
Advanced Materials, 1997
Communications and chromatographed on silica gel (70 g, eluent: EtOAcihexane, 1%) to give 5d as a pale yellow crystal; yield: 0.37 g (86 YO), m.p. 72-74 "C. MS, m/e 359 (Me, 100), 288 (21), 218 (62). 'H-NMR(CDC13, TMS [ppm]), 8.07 (lH, 2.5 Hz), 3.08 (4H, t, J = 7.9 Hz), 1.75-1.31 (16H, m), 0.89 (6H, t, J = 7.2 Hz).
Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes
Photochemical & Photobiological Sciences, 2012
We report the photophysical and electrochemical properties of phenol-pyrrolidino[60]fullerenes 1 and 2, in which the phenol hydroxyl group is ortho and para to the pyrrolidino group, respectively, as well as those of a phenyl-pyrrolidino[60]fullerene model compound, 3. For the ortho analog 1, the presence of an intramolecular hydrogen bond is supported by 1 H NMR and FTIR characterization. The redox potential of the phenoxyl radical-phenol couple in this architecture is 240 mV lower than that observed in the associated para compound 2. Further, the C 60 excited-state lifetime of the hydrogen-bonded compound 1 in benzonitrile is 260 ps, while the corresponding lifetime for 2 is identical to that of the model compound 3 at 1.34 ns. Addition of excess organic acid to a benzonitrile solution of 1 gives rise to a new species, 4, with an excited-state lifetime of 1.40 ns. In nonpolar aprotic solvents such as toluene, all three compounds have a C 60 excited-state lifetime of ∼1 ns. These results suggest that the presence of an intramolecular H-bond in 1 poises the potential of phenoxyl radical-phenol redox couple at a value that it is thermodynamically capable of reducing the photoexcited fullerene. This is not the case for the para analog 2 nor is it the case for the protonated species 4. This work illustrates that in addition to being used as light activated electron acceptors, pyrrolidino fullerenes are also capable of acting as built-in proton-accepting units that influence the potential of an attached donor when organized in an appropriate molecular design. † This article is published as part of a themed issue in honour of Professor Kurt Schaffner on the occasion of his 80th birthday. ‡ Current address:
Current Organic Chemistry, 2015
We review the fundamental properties and main applications of organic derivatives and complexes of fullerenes in the solid-state form. We address in particular the structural properties, in terms of crystal structure, polymorphism, orientational transitions and morphology, and the electronic structure and derived properties, such as chemical activity, electrical conduction mechanisms, optical properties, heat conduction and magnetism. The last two sections of the review focus on the solid-state optoelectronic and electrochemical applications of fullerene derivatives, which range from photovoltaic cells to field-effect transistors and photodetectors on one hand, to electron-beam resists, electrolytes and energy storage on the other.
Synthetic approaches towards the preparation of water-soluble fulleropyrrolidines
Carbon, 2000
Fullerene derivatives have interesting biological activities that make them good candidates for applications in medicinal chemistry. However, the development of these applications is hampered by the fact that fullerene derivatives are insoluble in water and polar media. We present here a general method for the preparation of N-functionalized fulleropyrrolidines with solubilizing groups via 1,3-dipolar cycloaddition of azomethine ylides to C .