Photoinduced PCET in ruthenium-phenol systems: thermodynamic equivalence of uni- and bidirectional reactions

Inorganic Chemistry
Julia Nomrowski, Oliver S Wenger

Abstract

Six termolecular reaction systems comprised of Ru(4,4′-bis(trifluoromethyl)-2,2′-bipyridine)32+, phenols with different para substituents, and pyridine in acetonitrile undergo proton-coupled electron transfer (PCET) upon photoexcitation of the metal complex. Five of these six phenols are found to release in concerted fashion an electron to the ruthenium photooxidant and a proton to the pyridine base. The kinetics for this concerted bidirectional PCET process and its relationship to the reaction free energy were compared to the driving-force dependence of reaction kinetics for unidirectional concerted proton–electron transfer (CPET) between the same phenols and Ru(2,2′-bipyrazine)32+, a combined electron/proton acceptor. The results strongly support the concept of thermodynamic equivalence between separated electron/proton acceptors and single-reagent hydrogen-atom acceptors. A key feature of the explored systems is the similarity between molecules employed for bi- and unidirectional CPET.

References

Jan 23, 2004·Chemical Communications : Chem Comm·Olof JohanssonBjörn Akermark
May 1, 2004·Annual Review of Physical Chemistry·James M Mayer
Oct 8, 2004·Journal of the American Chemical Society·Ian J Rhile, James M Mayer
Jan 29, 2005·Angewandte Chemie·Fabien LachaudAlly Aukauloo
Mar 25, 2006·The Journal of Organic Chemistry·Agnes KüttIlmar A Koppel
May 4, 2006·Journal of the American Chemical Society·Ian J RhileJames M Mayer
May 15, 2007·Journal of the American Chemical Society·Javier J ConcepcionThomas J Meyer
Mar 11, 2010·Proceedings of the National Academy of Sciences of the United States of America·Jeffrey J Warren, James M Mayer
Oct 12, 2010·Chemical Reviews·Jeffrey J WarrenJames M Mayer
Nov 6, 2010·Chemical Reviews·Sharon Hammes-Schiffer, Alexei A Stuchebrukhov
Apr 19, 2011·Organic & Biomolecular Chemistry·Julien BoninJean-Michel Savéant
Aug 5, 2011·Journal of the American Chemical Society·Ming-Tian ZhangLeif Hammarström
Sep 17, 2011·Journal of the American Chemical Society·Todd F MarkleJames M Mayer
Jun 19, 2012·Chemical Reviews·David R WeinbergThomas J Meyer
Feb 14, 2013·Accounts of Chemical Research·Oliver S Wenger
Jun 26, 2013·Journal of the American Chemical Society·Kyle T TarantinoRobert R Knowles
Sep 11, 2013·Accounts of Chemical Research·Cyrille CostentinCédric Tard
Apr 2, 2014·Chemical Reviews·Agostino MiglioreDavid N Beratan
Jul 22, 2014·Journal of the American Chemical Society·Thomas T Eisenhart, Jillian L Dempsey

❮ Previous
Next ❯

Citations

Dec 10, 2015·Journal of Fluorescence·Angusamy RajeswariSeenivasan Rajagopal
Jul 15, 2015·Journal of the American Chemical Society·Gilbert J Choi, Robert R Knowles
Jun 15, 2016·The Journal of Physical Chemistry Letters·Jovana MilićFrançois Diederich
Sep 24, 2016·Proceedings of the National Academy of Sciences of the United States of America·Christopher J GagliardiDavid W Thompson
Jul 4, 2017·Journal of the American Chemical Society·Wesley D Morris, James M Mayer
Apr 21, 2016·Physical Chemistry Chemical Physics : PCCP·Andrea Pannwitz, Oliver S Wenger
Jun 7, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Rahul V KhadeAvinash S Kumbhar
May 22, 2019·Chemistry : a European Journal·Jovana V Milić, François Diederich
Jul 11, 2019·Chemistry, an Asian Journal·Takafumi EnomotoShigeyuki Masaoka

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.