Luminescent Rhenium/Palladium Square Complex Exhibiting Excited State Intramolecular Electron Transfer Reactivity and Molecular Anion Sensing Characteristics

1995 ◽  
Vol 117 (47) ◽  
pp. 11813-11814 ◽  
Author(s):  
Robert V. Slone ◽  
Dong I. Yoon ◽  
Rebecca M. Calhoun ◽  
Joseph T. Hupp
Author(s):  
Carolin Müller ◽  
Ilse Friedländer ◽  
Benedikt Bagemihl ◽  
Sven Rau ◽  
Benjamin Dietzek

In situ spectroelectrochemical studies focussing on the Franck-Condon region and sub-ns electron transfer processes in Ru(II)-tpphz-Pt(II) based photocatalysts reveal that single-electron reduction effectively hinders intramolecular electron transfer between the photoexcited...


2019 ◽  
Vol 205 ◽  
pp. 09029
Author(s):  
Kristjan Kunnus ◽  
Lin Li ◽  
Marco Reinhard ◽  
Sergey Koroidov ◽  
Kasper S. Kjaer ◽  
...  

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.


2009 ◽  
Vol 08 (supp01) ◽  
pp. 1073-1086
Author(s):  
YUANZUO LI ◽  
SHASHA LIU ◽  
LILI ZHAO ◽  
MAODU CHEN ◽  
FENGCAI MA ◽  
...  

In this paper, the two-dimensional (2D) site and the three-dimensional (3D) cube representations [Sun MT, J Chem Phys124: 054903, 2006] have been further developed to study the charge transfer during excited-state relaxation. With these newly developed representations, we theoretically investigate the excited-state intramolecular electron transfer (ESIET) in enol excited-state geometry relaxation, and ESIET coupled with excited-state intramolecular proton transfer (ESIPT) in phototautomerization (in enol to keto transformation). The energy levels of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of HBODC in enol and keto absorption and fluorescence are compared to understand photoinduced ESIET and ESIPT process. The excited regions of molecule (where arrangement of electron density takes place during excited-state relaxation) are located with 2D site representation. 3D cube representations visualize the character of charge transfer (CT) in those regions. Results of the research indicate that the ability of charge transfer during enol excited-state geometry relaxation is much stronger than that in phototautomerization.


2008 ◽  
Vol 12 (09) ◽  
pp. 993-1004 ◽  
Author(s):  
Kei Ohkubo ◽  
Shunichi Fukuzumi

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.


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