Reorganization energies in organic π systems

Larsson, Sven; Klimkāns, Agris; Rodríguez‐Monge, Lucía; Duškesas, Grigorijus

doi:10.1016/s0166-1280(97)00216-9

Cited by 44 publications

(41 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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%

Creation of Fullerene-Based Artificial Photosynthetic Systems

Imahori¹

2007

Bulletin of the Chemical Society of Japan

156

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

Section: Introductionmentioning

confidence: 92%

Creation of Fullerene-Based Artificial Photosynthetic Systems

Imahori¹

2007

Bulletin of the Chemical Society of Japan

156

View full text Add to dashboard Cite

show abstract

“…C 60 possesses eight accessible oxidation states [158–161] and has small inner-sphere reorganization energy (~0.06 eV) [162,163]. This low λ i is most often cited as the attribute of C 60 that leads to efficient photoinduction of a long-lived charge-separated state.…”

Section: Redox Species Used For Electrochemical Determination Of Kmentioning

confidence: 99%

Electrochemistry of redox-active self-assembled monolayers

Eckermann

Feld

Shaw

et al. 2010

Coordination Chemistry Reviews

530

492

View full text Add to dashboard Cite

Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redoxactivated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C 60 ). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs.

show abstract

“…Support for these remarkably small l V values also derives from an earlier theoretical calculation of the vibrational reorganization energy of C 60 (l V 0.06 eV). [31] The p-stacked dyad reveals a notably larger value, which is indicative of the perturbation due to the overlapping p-systems. This conclusion is in agreement with the relatively strong coupling estimated for this donor ± acceptor ensemble (vide supra).…”

mentioning

confidence: 97%

Modulating Charge‐Transfer Interactions in Topologically Different Porphyrin–C₆₀ Dyads

Guldi

Hirsch

Scheloske

et al. 2003

Chemistry A European J

117

View full text Add to dashboard Cite

Control over the interchromophore separation, their angular relationship, and the spatial overlap of their electronic clouds in several ZnP-C(60) dyads (ZnP=zinc porphyrin) is used to modulate the rates of intramolecular electron transfer. For the first time, a detailed analysis of the charge transfer absorption and emission spectra, time-dependent spectroscopic measurements, and molecular dynamics simulations prove quantitatively that the same two moieties can produce widely different electron-transfer regimes. This investigation also shows that the combination of ZnP and C(60) consistently produces charge recombination in the inverted Marcus region, with reorganization energies that are remarkably low, regardless of the solvent polarity. The time constants of electron transfer range from the mus to the ps regime, the electronic couplings from a few tens to several hundreds of cm(-1), and the reorganization energies remain below 0.54 eV and can be as low as 0.16 eV.

show abstract

Reorganization energies in organic π systems

Cited by 44 publications

References 22 publications

Creation of Fullerene-Based Artificial Photosynthetic Systems

Creation of Fullerene-Based Artificial Photosynthetic Systems

Electrochemistry of redox-active self-assembled monolayers

Modulating Charge‐Transfer Interactions in Topologically Different Porphyrin–C₆₀ Dyads

Contact Info

Product

Resources

About

Reorganization energies in organic π systems

Cited by 44 publications

References 22 publications

Creation of Fullerene-Based Artificial Photosynthetic Systems

Creation of Fullerene-Based Artificial Photosynthetic Systems

Electrochemistry of redox-active self-assembled monolayers

Modulating Charge‐Transfer Interactions in Topologically Different Porphyrin–C60 Dyads

Contact Info

Product

Resources

About

Modulating Charge‐Transfer Interactions in Topologically Different Porphyrin–C₆₀ Dyads