Electron-Transfer Properties of C60 and tert-Butyl-C60 Radical

Fukuzumi, Shunichi; Nakanishi, Ikuo; Suenobu, Tomoyoshi; Kadish, Karl M.

doi:10.1021/ja9838615

Cited by 80 publications

(78 citation statements)

References 65 publications

(59 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[37] All ESR measurements were performed on a JEOL X-band spectrometer (JES-ME-1X) with a quartz ESR tube (3.9 mm i.d.). The g values and hyperfine splitting constants were calibrated using an Mn 2 + marker.…”

Section: Methodsmentioning

confidence: 99%

Long‐Lived Charge‐Separated State Generated in a Ferrocene–meso,meso‐Linked Porphyrin Trimer–Fullerene Pentad with a High Quantum Yield

Imahori

Sekiguchi

Kashiwagi

et al. 2004

Chemistry A European J

Self Cite

205

132

View full text Add to dashboard Cite

A meso,meso-linked porphyrin trimer, (ZnP)3, as a light-harvesting chromophore, has been incorporated for the first time into a photosynthetic multistep electron-transfer model including ferrocene (Fc) as an electron donor and fullerene (C60) as an electron acceptor, to construct the ferrocene-meso,meso-linked porphyrin trimer-fullerene system Fc-(ZnP)3-C60. Photoirradiation of Fc-(ZnP)3-C60 results in photoinduced electron transfer from both the singlet and triplet excited states of the porphyrin trimer, 1(ZnP)3* and 3(ZnP)3*, to the C60 moiety to produce the porphyrin trimer radical cation-C60 radical anion pair, Fc-(ZnP)3*+-C60*-. Subsequent formation of the final charge-separated state Fc+-(ZnP)3-C60*- was confirmed by the transient absorption spectra observed by pico- and nanosecond time-resolved laser flash photolysis. The final charge-separated state decays, obeying first-order kinetics, with a long lifetime (0.53 s in DMF at 163 K) that is comparable with that of the natural bacterial photosynthetic reaction center. More importantly, the quantum yield of formation of the final charge-separated state (0.83 in benzonitrile) remains high, despite the large separation distance between the Fc+ and C60*- moieties. Such a high quantum yield results from efficient charge separation through the porphyrin trimer, whereas a slow charge recombination is associated with the localized porphyrin radical cation in the porphyrin trimer. The light-harvesting efficiency in the visible region has also been much improved in Fc-(ZnP)3-C60 because of exciton coupling in the porphyrin trimer as well as an increase in the number of porphyrins.

show abstract

Section: Methodsmentioning

confidence: 99%

Long‐Lived Charge‐Separated State Generated in a Ferrocene–meso,meso‐Linked Porphyrin Trimer–Fullerene Pentad with a High Quantum Yield

Imahori

Sekiguchi

Kashiwagi

et al. 2004

Chemistry A European J

Self Cite

205

132

View full text Add to dashboard Cite

show abstract

“…A small v of C 60 (0.06 eV) has also been obtained from theoretical calculation. [131][132][133] In addition to the 1996 reports of the small of fullerenes, Guldi and Asmus have also reported relatively small values for C 76 and C 78 in intermolecular ET using pulse radiolysis. 134 The values of C 76 and C 78 (ca.…”

Section: Introductionmentioning

confidence: 92%

“…The rather large value is similar to those for an intermolecular electron self-exchange reaction of tBuC 60 À /tBuC 60 in benzonitrile/benzene (1/7 = v/v) (0.64 eV) and for BQ/ BQ À couple in benzonitrile (0.74 eV). 133 In contrast, values (%0:3 eV) for an intermolecular electron self-exchange reaction of porphyrins and NIm in acetonitrile are much smaller than the value for fullerenes. 79 Intermolecular ET involving spherical three-dimensional fullerenes is likely to occur at large separation distances rendering the intermolecular large.…”

Section: Introductionmentioning

confidence: 94%

Creation of Fullerene-Based Artificial Photosynthetic Systems

Imahori¹

2007

Bulletin of the Chemical Society of Japan

154

View full text Add to dashboard Cite

Various porphyrin-fullerene-linked systems have been prepared to elucidate the intrinsic electron-transfer properties of fullerenes. Photodynamical studies on porphyrin-fullerene-linked systems showed that spherical fullerenes accelerated photoinduced electron transfer and charge-shift, but slowed down charge recombination, which is in sharp contrast with those of conventional planar acceptors such as quinones and imides. For the first time, it was shown that the unique electron-transfer properties result from the small reorganization energies of fullerenes arising from the delocalized system on the sphere together with the rigid structure. The small reorganization energies make it possible to produce a long-lived charge-separated state with a high quantum yield in donor-fullerene systems. The finding also will allow us to construct light energy conversion systems as well as artificial photosynthetic models. Highly efficient photoinduced energy and electron transfer were achieved on gold and ITO electrodes modified with self-assembled monolayers of the porphyrin-fullerene-linked systems. We also developed dye-sensitized bulk heterojunction solar cell possessing both characteristics of dye-sensitized and bulk heterojunction solar cells. These results showed the advantages of fullerenes as electron acceptors in artificial photosynthetic model, photonic molecular devices and machines, and organic molecular electronics including solar cells.

show abstract

“…From a study of their electron transfer rates, C 60 -and C 60 2-have been usefully compared to the pbenzoquinone/semiquinone one-electron couple. 424 Electron self-exchange rates in fullerides are fast because the t 1u electrons are delocalized and accessible and because nuclear reorganization is small. 199 In summary, because of delocalized charge there is little evidence for classical nucleophilic behavior of fullerides, although this does not thwart the addition of electrophiles via electron transfer pathways.…”

Section: Fulleride Nucleophilicity/electron Transfermentioning

confidence: 99%

Discrete Fulleride Anions and Fullerenium Cations

2000

View full text Add to dashboard Cite

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.

show abstract

Electron-Transfer Properties of C₆₀ and tert-Butyl-C₆₀ Radical

Cited by 80 publications

References 65 publications

Long‐Lived Charge‐Separated State Generated in a Ferrocene–meso,meso‐Linked Porphyrin Trimer–Fullerene Pentad with a High Quantum Yield

Long‐Lived Charge‐Separated State Generated in a Ferrocene–meso,meso‐Linked Porphyrin Trimer–Fullerene Pentad with a High Quantum Yield

Creation of Fullerene-Based Artificial Photosynthetic Systems

Discrete Fulleride Anions and Fullerenium Cations

Contact Info

Product

Resources

About