Reversible Fullerene Electrochemistry: Correlation with the HOMO-LUMO Energy Difference for C60, C70, C76, C78, and C84

Yang, Yifan; Arias, Francisco J.; Echegoyen, Luis; Chibante, L. P. F.; Flanagan, Scott; Robertson, A.; Wilson, Lon J.

doi:10.1021/ja00134a027

Cited by 155 publications

(125 citation statements)

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“…It is a particular feature of fullerenes as a class of molecules, reflecting their delocalized LUMOs, and is observed in C 70 , C 76 , C 78 , and C 84 . 9,51,[55][56][57][58][59] It has also been calculated using density functional theory. 60 Table 1 lists representative redox data for the more commonly known fullerenes.…”

Section: A Reductive Voltammetrymentioning

confidence: 99%

“…24 For a number of fullerenes, there is a good correlation between the calculated HOMO-LUMO gap and the "electrochemical gap", i.e., the difference between the first reduction potential and the first oxidation potential. 57 The effect of the medium on the redox potentials of C 60 has been studied by a number of groups. Independent studies by Fawcett, 68 Kadish,69,70 Bard, 71 and Compton 72 reveal a significant influence of the cation on the kinetics and, to a lesser extent, the thermodynamics of the first electron transfer to C 60 .…”

Section: A Reductive Voltammetrymentioning

confidence: 99%

“…Although initially believed to form at an unusually low potential, 87 C 76 + is now known to form reversibly at 0.81 V. 57 The C 2v and D 3 isomers of C 78 oxidize at 0.95 and 0.70 V, respectively. 57 C 84 has a number of isomers, all of which oxidize around 0.9 V. 57,59 A short review on the redox potentials of the higher fullerenes has appeared. 88 In keeping with their delocalized charges, the first oxidation potentials of C 60 , C 70 , C 76 , and C 78 follow the same trend as their first ionization potentials (7.61, 7.58, 7.10, and 7.05 eV, respectively).…”

Section: +mentioning

confidence: 99%

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Discrete Fulleride Anions and Fullerenium Cations

2000

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His research interests include reactive cation and superacid chemistry with inert carborane counterions, ionic liquids, bioinorganic chemistry, spin-coupling phenomena, fullerene chemistry, and new carbon-or porphyrin-based materials. He is a Sloan Fellow, a Dreyfus Teacher−Scholar Awardee, and a Guggenheim Fellow. Robert Bolskar received his B.S. degree in Chemistry from Carroll College in Waukesha, WI, in 1992. He earned his Ph.D. degree at the University of Southern California in Los Angeles under the direction of Christopher Reed in 1997, investigating the synthetic redox chemistry of fullerene anions and cations. In 1998 he moved to the University of California, Riverside, as Managing Research Associate. He is currently Senior Chemist at TDA Research in Wheat Ridge, CO. His research interests include the chemistry and physics of fullerene compounds, supramolecular chemistry, strongly oxidizing systems, and electrophilic cations.

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Section: A Reductive Voltammetrymentioning

confidence: 99%

Section: A Reductive Voltammetrymentioning

confidence: 99%

Section: +mentioning

confidence: 99%

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Discrete Fulleride Anions and Fullerenium Cations

2000

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“…The IPR can explain the high stability of C 60 fullerene structure whose 12 pentagons are completely surrounded by hexagons, as well as predict successfully the stable fullerenes with "magic number" n = 32, 36, 50, 60, 70, 76, 78, and 84. [3][4][5][6][7][8][9][10][11][12][13] The IPR can be theoretically rationalized on both steric and -electronic grounds. Fullerenes with three-, four-, and seven-membered rings ͑3-, 4-, and 7-MRs͒ are reasonably ruled out due to extra local steric strain and loss of -delocalization.…”

Section: Introductionmentioning

confidence: 99%

“…21 There have been increasing research interests in small to medium-sized ͑n =20-36͒ carbon clusters since the discovery of the C 60 . [7][8][9][10][11][12][13]17,[22][23][24][25][26][27][28][29][30][31] In our previous paper ͑Paper I 26 ͒, we studied relative stabilities of various isomers of carbon cluster C 20 using high-level ab initio methods. In that study, the bowl-shaped "fullerene fragment" corannulene was theoretically identified as the ground-state isomer of C 20 , which has a lower energy than the ͑only͒ classical fullerene isomer of C 20 .…”

Section: Introductionmentioning

confidence: 99%

Ab initio calculation of carbon clusters. II. Relative stabilities of fullerene and nonfullerene C24

Shao

Bulusu

et al. 2008

The Journal of Chemical Physics

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Chemical stabilities of six low-energy isomers of C 24 derived from global-minimum search are investigated. The six isomers include one classical fullerene ͑isomer 1͒ whose cage is composed of only five-and six-membered rings ͑5 / 6-MRs͒, three nonclassical fullerene structures whose cages contain at least one four-membered ring ͑4-MR͒, one plate, and one monocyclic ring. Chemical and electronic properties of the six C 24 isomers are calculated based on a density-functional theory method ͑hybrid PBE1PBE functional and cc-pVTZ basis set͒. The properties include the nucleus-independent chemical shifts ͑NICS͒, singlet-triplet splitting, electron affinity, ionization potential, and gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital ͑HOMO-LUMO͒ gap. The calculation suggests that the neutral isomer 2, a nonclassical fullerene with two 4-MRs, may be more chemically stable than the classical fullerene ͑isomer 1͒. Analyses of molecular orbital NICS show that the incorporations of 4-MRs into the cage considerably reduce paratropic contributions from HOMO, HOMO-1, and HOMO-2, which are mainly responsible for the sign change in NICS from positive for isomer 1 ͑42͒ to negative ͑−19͒ for isomer 2, although C 24 clusters satisfy neither 4N + 2 nor 2͑N +1͒ 2 aromaticity rule. Anion photoelectron spectra of four cage isomers, one plate, one monocyclic ring, and one tadpole isomer, as well as three bicyclic ring isomers are calculated. The simulated photoelectron spectra of monoand bicyclic rings ͑with C 1 symmetry͒ appear to match the measured HOMO-LUMO gap ͑between the first and second band in the experimental spectra͒ ͓S. Yang et al., Chem. Phys. Lett. 144, 431 ͑1988͔͒. Nevertheless, the nonclassical fullerene isomers 3 and 4 apparently also match the measured vertical detachment energy ͑2.90 eV͒ reasonably well. These results suggest possible coexistence of nonclassical fullerene isomers with the mono-and bicyclic ring isomers of C 24 − under the experimental conditions.

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