A Continuum of Proton-Coupled Electron Transfer Reactivity DOI
Julia W. Darcy, Brian Koronkiewicz, Giovanny A. Parada

et al.

Accounts of Chemical Research, Journal Year: 2018, Volume and Issue: 51(10), P. 2391 - 2399

Published: Sept. 20, 2018

ConspectusProton-coupled electron transfer (PCET) covers a wide range of reactions involving the transfer(s) electrons and protons. The best-known PCET reaction, hydrogen atom (HAT), has been studied in detail for more than century. HAT is generally described as concerted (H• ≡ H+ + e–) from one group to another, Y H–X → Y–H X, but strict definition difficult establish. Distinctions are challenging when "H•" involves e– that to/from spatially distinct sites or even completely separate reagents (multiple-site proton–electron transfer, MS-CPET). MS-CPET reactivity increasingly proposed biological synthetic contexts, some typically resemble MS-CPET. Despite "look different," we argue here these lie on continuum, they governed by many same key parameters. This Account walks reader across this using series studies show strong similarities move protons seemingly different ways.To prepare our stroll, describe thermochemical kinetic frameworks driving force solution reaction most easily discussed difference bond dissociation free energies (BDFEs) reactants products. BDFEs can be analyzed sums proton steps therefore obtained pKa E° values. Even though do not make break bonds way HAT, description used with introduction an effective BDFE (BDFEeff). BDFEeff reductant/acid pair energy form H•, which values analogous fashion standard BDFE. When thermochemistry known, rate constants understood often predicted linear relationships (the Brønsted catalysis law) Marcus theory type approaches.After background, walk through continuum reactivity. Our journey begins study metal-mediated hydrocarbon substrates metal-oxo complex travels end spectrum, hydroxylamine TEMPOH two molecules. These examples, those between, all within thermodynamic framework. A first examples C–H uses framework highlights importance bonding preorganization. analyses along similar different, attempts divide into subcategories obscure much essential chemistry. We hope developing common features will help experts newcomers alike explore exciting new territories

Language: Английский

Proton-Coupled Electron Transfer DOI

David R. Weinberg,

Christopher J. Gagliardi,

Jonathan F. Hull

et al.

Chemical Reviews, Journal Year: 2012, Volume and Issue: 112(7), P. 4016 - 4093

Published: June 18, 2012

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTProton-Coupled Electron TransferDavid R. Weinberg†§, Christopher J. Gagliardi†, Jonathan F. Hull†, Christine Fecenko Murphy‡, Caleb A. Kent†, Brittany C. Westlake∥, Amit Paul†, Daniel H. Ess†, Dewey Granville McCafferty*‡, and Thomas Meyer*†View Author Information† Department of Chemistry, University North Carolina at Chapel Hill, 27599-3290, United States‡ B219 Levine Science Research Center, Box 90354, Duke University, Durham, 27708-0354, States§ Physical Environmental Sciences, Colorado Mesa 1100 Avenue, Grand Junction, 81501-3122, States∥ The American Chemical Society, 1155 Sixteenth Street NW, Washington, District Columbia 20036, States*E-mail: [email protected]Cite this: Chem. Rev. 2012, 112, 7, 4016–4093Publication Date (Web):June 18, 2012Publication History Received19 May 2011Published online18 June 2012Published inissue 11 July 2012https://pubs.acs.org/doi/10.1021/cr200177jhttps://doi.org/10.1021/cr200177jreview-articleACS PublicationsCopyright © 2012 SocietyRequest reuse permissionsArticle Views44915Altmetric-Citations1339LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated to reflect usage leading up last few days.Citations number other articles citing this article, calculated by Crossref daily. Find more information about citation counts.The Altmetric Attention Score is a quantitative measure attention that research has received online. Clicking on donut icon will load page altmetric.com with additional details score social media presence for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Charge transfer,Oxidation,Proton coupled electron transfer,Reaction mechanisms,Redox reactions Get e-Alerts

Language: Английский

Citations

2275
Visible‐Light Photocatalysis: Does It Make a Difference in Organic Synthesis? DOI Open Access
Leyre Marzo, Santosh K. Pagire, Oliver Reiser

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(32), P. 10034 - 10072

Published: Feb. 21, 2018

Visible-light photocatalysis has evolved over the last decade into a widely used method in organic synthesis. Photocatalytic variants have been reported for many important transformations, such as cross-coupling reactions, α-amino functionalizations, cycloadditions, ATRA or fluorinations. To help chemists select photocatalytic methods their synthesis, we compare this Review classical and procedures selected classes of reactions highlight advantages limitations. In cases, proceed under milder reaction conditions, typically at room temperature, stoichiometric reagents are replaced by simple oxidants reductants, air, oxygen, amines. Does visible-light make difference synthesis? The prospect shuttling electrons back forth to substrates intermediates selectively transfer energy through visible-light-absorbing photocatalyst holds promise improve current radical chemistry open up new avenues accessing reactive species hitherto unknown, especially merging with organo- metal catalysis.

Language: Английский

Citations

1808
Theory of multiple proton–electron transfer reactions and its implications for electrocatalysis DOI
Marc T. M. Koper

Chemical Science, Journal Year: 2013, Volume and Issue: 4(7), P. 2710 - 2710

Published: Jan. 1, 2013

This perspective article outlines a simple but general theoretical analysis for multiple proton–electron transfer reactions, based on the microscopic theory of proton-coupled electron recent developments in thermodynamic multi-step and experimental realization that many reactions feature decoupled steps their mechanism. It is shown decoupling proton leads to strong pH dependence overall catalytic reaction, implying an optimal high turnover, associated catalyst at pH. When more than one intermediate involved, scaling relationships between intermediates may dictate limit extent reversibility be achievable reaction. The discussed relation results number redox are importance sustainable energy conversion, primarily focusing dependence.

Language: Английский

Citations

743
Polyoxometalate water oxidation catalysts and the production of green fuel DOI
Hongjin Lv, Yurii V. Geletii,

Chongchao Zhao

et al.

Chemical Society Reviews, Journal Year: 2012, Volume and Issue: 41(22), P. 7572 - 7572

Published: Jan. 1, 2012

In the last five years and currently, research on solar fuels has been intense no sub-area in this field more active than development of water oxidation catalysts (WOCs). timeframe, a new class molecular based polyoxometalates have reported that combine advantages homogeneous heterogeneous catalysts. This review addresses central issues green energy generation, challenges catalyst development, possible uses science.

Language: Английский

Citations

728
Excited-state proton coupled charge transfer modulated by molecular structure and media polarization DOI
Alexander P. Demchenko,

Kuo‐Chun Tang,

Pi‐Tai Chou

et al.

Chemical Society Reviews, Journal Year: 2012, Volume and Issue: 42(3), P. 1379 - 1408

Published: Nov. 21, 2012

Charge and proton transfer reactions in the excited states of organic dyes can be coupled many different ways. Despite complementarity charges, they occur on time scales directions molecular framework. In certain cases, excited-state equilibrium established between charge-transfer proton-transfer species. The interplay these modulated even reversed by variations dye structures changes surrounding media. With knowledge mechanisms processes, desired rates achieved, thus multiple emission spectral features harnessed. These have found versatile applications a number cutting-edge technological areas, particularly fluorescence sensing imaging.

Language: Английский

Citations

681
The PYXAID Program for Non-Adiabatic Molecular Dynamics in Condensed Matter Systems DOI
Alexey V. Akimov, Oleg V. Prezhdo

Journal of Chemical Theory and Computation, Journal Year: 2013, Volume and Issue: 9(11), P. 4959 - 4972

Published: Oct. 14, 2013

This work introduces the PYXAID program, developed for non-adiabatic molecular dynamics simulations in condensed matter systems. By applying classical path approximation to fewest switches surface hopping approach, we have an efficient computational tool that can be applied study photoinduced at ab initio level systems composed of hundreds atoms and involving thousands electronic states. The technique is used detail ultrafast relaxation hot electrons crystalline pentacene. simulated occurs on a 500 fs time scale, excellent agreement with experiment, driven by lattice vibrations 200–250 cm–1 frequency range. program organized as Python extension module easily combined other Python-driven modules, enhancing user-friendliness flexibility software. source code additional information are available Web address http://gdriv.es/pyxaid. released under GNU General Public License.

Language: Английский

Citations

680
Hydrogen Atom Transfer (HAT): A Versatile Strategy for Substrate Activation in Photocatalyzed Organic Synthesis DOI Creative Commons
Luca Capaldo, Davide Ravelli

European Journal of Organic Chemistry, Journal Year: 2017, Volume and Issue: 2017(15), P. 2056 - 2071

Published: March 2, 2017

The adoption of hydrogen atom transfer (HAT) in a photocatalytic approach, which an excited catalyst is responsible for substrate activation, offers unique opportunities organic synthesis, enabling the straightforward activation R–H (R = C, Si, S) bonds desired reagents. Either direct strategy, based on intrinsic reactivity limited number photocatalysts state, or indirect one, cycle used generation thermal abstractor, can be exploited. This microreview summarizes most recent advances (mainly from last two years) this rapidly developing area research, collecting selected examples according to nature species promoting HAT process. From synthetic point view, has led development plethora strategies C–C, C–Si, C–N, C–S, and C–halogen (particularly, fluorine) bond formation, as well oxidation reactions.

Language: Английский

Citations

648
Theoretical Insights into Photoinduced Charge Transfer and Catalysis at Oxide Interfaces DOI
Alexey V. Akimov, Amanda J. Neukirch, Oleg V. Prezhdo

et al.

Chemical Reviews, Journal Year: 2013, Volume and Issue: 113(6), P. 4496 - 4565

Published: April 29, 2013

ADVERTISEMENT RETURN TO ISSUEPREVReviewTheoretical Insights into Photoinduced Charge Transfer and Catalysis at Oxide InterfacesAlexey V. Akimov†‡, Amanda J. Neukirch§, Oleg Prezhdo*†View Author Information† Department of Chemistry, University Rochester, New York 14627, United States‡ Chemistry Department, Brookhaven National Laboratory, Upton, 11973-5000, States§ Physics Astronomy, States*E-mail: [email protected]Cite this: Chem. Rev. 2013, 113, 6, 4496–4565Publication Date (Web):April 29, 2013Publication History Received11 December 2012Published online29 April 2013Published inissue 12 June 2013https://pubs.acs.org/doi/10.1021/cr3004899https://doi.org/10.1021/cr3004899review-articleACS PublicationsCopyright © 2013 American Chemical SocietyRequest reuse permissionsArticle Views11904Altmetric-Citations446LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated to reflect usage leading up last few days.Citations number other articles citing this article, calculated by Crossref daily. Find more information about citation counts.The Altmetric Attention Score is a quantitative measure attention that research has received online. Clicking on donut icon will load page altmetric.com with additional details score social media presence for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Charge transfer,Dyes pigments,Electrical energy,Oxides,Semiconductors Get e-Alerts

Language: Английский

Citations

497
Biochemistry and Theory of Proton-Coupled Electron Transfer DOI Creative Commons
Agostino Migliore, Nicholas F. Polizzi, Michael J. Therien

et al.

Chemical Reviews, Journal Year: 2014, Volume and Issue: 114(7), P. 3381 - 3465

Published: April 1, 2014

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTBiochemistry and Theory of Proton-Coupled Electron TransferAgostino Migliore*†, Nicholas F. Polizzi‡, Michael J. Therien†, David N. Beratan*†‡§View Author Information†Department Chemistry, ‡Department Biochemistry, §Department Physics, Duke University, Durham, North Carolina 27708, United States*Phone: 919-660-1556. E-mail: [email protected]*Phone: 919-660-1526. protected]Cite this: Chem. Rev. 2014, 114, 7, 3381–3465Publication Date (Web):April 1, 2014Publication History Received19 November 2013Published online1 April 2014Published inissue 9 2014https://doi.org/10.1021/cr4006654Copyright © 2014 American Chemical SocietyRIGHTS & PERMISSIONSACS AuthorChoiceArticle Views10346Altmetric-Citations308LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated to reflect usage leading up last few days.Citations number other articles citing this article, calculated by Crossref daily. Find more information about citation counts.The Altmetric Attention Score is a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InReddit (14 MB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting SUBJECTS:Free energy,Charge transfer,Proton coupled electron transfer,Wave function,Solvents e-Alerts

Language: Английский

Citations

464
Quantum Mechanical Studies on the Photophysics and the Photochemistry of Nucleic Acids and Nucleobases DOI
Roberto Improta, Fabrizio Santoro, Lluı́s Blancafort

et al.

Chemical Reviews, Journal Year: 2016, Volume and Issue: 116(6), P. 3540 - 3593

Published: March 1, 2016

The photophysics and photochemistry of DNA is great importance due to the potential damage genetic code by UV light. Quantum mechanical studies have played a key role in interpretating results modern time-resolved pump-probe spectroscopy, elucidating main photoactivated reactive paths. This review provides concise, complete picture computational carried out, approximately, past decade. We start with an overview nucleobases gas phase solution. discuss proposed mechanisms for ultrafast decay ground state, that involve conical intersections, consider triplet states, analyze how solvent modulates photophysics. Then we move larger systems, from dinucleotides single- double-stranded oligonucleotides. focus on possible charge transfer delocalized or excitonic states these systems photochemical finish outlook current challenges field future directions research.

Language: Английский

Citations

451