Metal Ion-Promoted Intramolecular Electron Transfer in a Ferrocene-Naphthoquinone Linked Dyad. Continuous Change in Driving Force and Reorganization Energy with Metal Ion Concentration

2003 ◽  
Vol 125 (23) ◽  
pp. 7014-7021 ◽  
Author(s):  
Ken Okamoto ◽  
Hiroshi Imahori ◽  
Shunichi Fukuzumi
Keyword(s):  
Electron Transfer ◽  
Driving Force ◽  
Metal Ion ◽  
Reorganization Energy ◽  
Ion Concentration ◽  
Intramolecular Electron Transfer ◽  
Continuous Change

scholarly journals Solvatochromic and Ligand Effects in Ultrafast Intramolecular Electron Transfer in Fe-based Molecular Photosensitizers

2019 ◽  
Vol 205 ◽  
pp. 09029
Author(s):  
Kristjan Kunnus ◽  
Lin Li ◽  
Marco Reinhard ◽  
Sergey Koroidov ◽  
Kasper S. Kjaer ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Charge Transfer ◽  
Driving Force ◽  
Reorganization Energy ◽  
The Other ◽  
Intramolecular Electron Transfer ◽  
Ligand Effects ◽  
Ligand Charge Transfer ◽  
Excited State Lifetimes

Metal-to-ligand charge-transfer (MLCT) excited state lifetimes of [Fe(CN)4(2,2’-bipyridine)]2- and [Fe(CN)4(2,3-bis(2-pyridyl)pyrazine)]2-exhibit strong solvent and ligand dependence. We conclude that these effects can be described with Marcus-like model where changes in the MLCT energy correspond directly to the changes in the electron transfer driving force and all the other factors (e.g. reorganization energy) can be considered constant.

Long-lived charge-separated states of simple electron donor-acceptor dyads using porphyrins and phthalocyanines

2008 ◽  
Vol 12 (09) ◽  
pp. 993-1004 ◽  
Author(s):  
Kei Ohkubo ◽  
Shunichi Fukuzumi
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Electron Donor ◽  
Driving Force ◽  
Reorganization Energy ◽  
Charge Recombination ◽  
Zinc Phthalocyanine ◽  
Intramolecular Electron Transfer ◽  
Triplet Excited State ◽  
Donor Acceptor

Control of electron-transfer processes is described for a number of electron donor-acceptor dyads containing porphyrins or phthalocyanines as models for the photosynthetic reaction center. The rates for intramolecular electron transfer in the dyads are controlled by the driving force and reorganization energy of electron transfer. The small reorganization energy of electron transfer reactions and large driving force of charge recombination are required to form long-lived charge-separated states. A directly linked zinc chlorin-fullerene dyad, especially, has the longest lifetime of charge-separated state at 120 s at -150 °C, which is a much longer lifetime and higher energy than those of natural photosynthetic reaction centers. On the other hand, the charge-separated states of the phthalocyanine-based donor-acceptor dyads (silicon phthalocyanine-fullerene, and zinc phthalocyanine-perylenebisimide) are short-lived since charge recombination forms the low-lying triplet excited state of the chromophore. The energy of the charge-separated state of a zinc phthalocyanine-perylenebisimide dyad is decreased by binding of metal ions to the radical anion moiety in order to be lower than the triplet excited state. This results in formation of a long-lived charge-separated state. The mechanistic viability of formation of long-lived charge-separated states is demonstrated by a variety of examples based on the Marcus theory of electron transfer.

Small Reorganization Energy of Intramolecular Electron Transfer in Fullerene-Based Dyads with Short Linkage

2002 ◽  
Vol 106 (46) ◽  
pp. 10991-10998 ◽  
Author(s):  
Kei Ohkubo ◽  
Hiroshi Imahori ◽  
Jianguo Shao ◽  
Zhongping Ou ◽  
Karl M. Kadish ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Intramolecular Electron Transfer

Dependence of Intramolecular Electron-Transfer Rates on Driving Force, pH, and Temperature in Ammineruthenium-Modified Ferrocytochromesc

1997 ◽  
Vol 101 (4) ◽  
pp. 687-693 ◽  
Author(s):  
James F. Wishart ◽  
Ji Sun ◽  
Myung Cho ◽  
Chang Su ◽  
Stephan S. Isied
Keyword(s):  
Electron Transfer ◽  
Driving Force ◽  
Intramolecular Electron Transfer ◽  
Transfer Rates

Effects of Hydrogen Bonding on Metal Ion-Promoted Intramolecular Electron Transfer and Photoinduced Electron Transfer in a Ferrocene-Quinone Dyad with a Rigid Amide Spacer

2003 ◽  
Vol 125 (4) ◽  
pp. 1007-1013 ◽  
Author(s):  
Shunichi Fukuzumi ◽  
Ken Okamoto ◽  
Yutaka Yoshida ◽  
Hiroshi Imahori ◽  
Yasuyuki Araki ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Hydrogen Bonding ◽  
Photoinduced Electron Transfer ◽  
Metal Ion ◽  
Intramolecular Electron Transfer

scholarly journals Catalytic control of electron-transfer processes

2003 ◽  
Vol 75 (5) ◽  
pp. 577-587 ◽  
Author(s):  
Shunichi Fukuzumi
Keyword(s):  
Electron Transfer ◽  
Metal Ions ◽  
Metal Ion ◽  
Photochemical Reactions ◽  
Transfer Reactions ◽  
Intramolecular Electron Transfer ◽  
Radical Anions ◽  
Electron Transfer Reactions ◽  
Transfer Processes ◽  
Electron Transfer Processes

Catalytic control of electron-transfer processes is described for a number of photoinduced and thermal electron-transfer reactions, including back electron transfer in the charge-separated state of artificial photosynthetic compounds. The intermolecular and intramolecular electron-transfer processes are accelerated by complexation of radical anions, produced in the electron transfer, with metal ions that act as Lewis acids. Quantitative measures to determine the Lewis acidity of a variety of metal ions are given in relation with the promoting effects of metal ions in the electron-transfer reactions. The mechanistic viability of metal ion catalysis in electron-transfer reactions is demonstrated by a variety of examples of both thermal and photochemical reactions that involve metal ion-promoted electron-transfer processes as the rate-determining steps, which are made possible to proceed by complexation of radical anions with metal ions.

Intramolecular Electron Transfer within the Substituted Tetrathiafulvalene−Quinone Dyads:  Facilitated by Metal Ion and Photomodulation in the Presence of Spiropyran

2007 ◽  
Vol 129 (21) ◽  
pp. 6839-6846 ◽  
Author(s):  
Hui Wu ◽  
Deqing Zhang ◽  
Lei Su ◽  
Kei Ohkubo ◽  
Chunxi Zhang ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Metal Ion ◽  
Intramolecular Electron Transfer

Intramolecular electron transfer in cyclopeptide involving tryptophan and tyrosine and corrected two-sphere model for solvent reorganization energy

2005 ◽  
Vol 312 (1-3) ◽  
pp. 21-29 ◽  
Author(s):  
Jin Tang ◽  
Xiang-Yuan Li ◽  
Ke-Xiang Fu ◽  
Ji-Feng Liu ◽  
Shen-Zhuang Lu
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Intramolecular Electron Transfer ◽  
Sphere Model ◽  
Solvent Reorganization Energy
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