Author: Trevor Safko
Publisher:
ISBN:
Category : Chemistry
Languages : en
Pages : 282
Book Description
The coupling of proton and electron transfers in concerted or sequential processes is of central importance to many biochemical and catalytic reactions. In this context, proton-coupled electron transfer reactions are typically described electrochemically, whereby the transfer of a proton is coordinated to a change in the oxidation state of the constituent donor/acceptor pairs. In the excited-state, intermolecular proton transfers are often facilitated through a redistribution of electron-density (charge-transfer) along the proton-transfer reaction coordinate without a corresponding change in the oxidation state of the donor/acceptor pair. Distinguishing charge-transfer from full electron-transfer reactions along the excited-state potential energy surface has received increased attention as advancements in engineering allow for the interrogation of the fastest molecular events. This dissertation seeks primarily to examine the confluence of charge-transfer, electron-transfer, and proton-transfer reactions which occur adiabatically in the excited-states of N, N-dimethyl-3-arylpropan-1-ammonium salts in solution. For these compounds, an excited-state intermolecular proton-transfer to the solvent is accompanied by intramolecular charge-transfer and the formation of either an emissive exciplex or a transient solvent-separated ion pair. The various electronic configurations have been interrogated through an array of spectroscopic techniques in order to more thoroughly understand the convergence of thermodynamic and kinetic factors affecting the proposed mechanism. In this regard, a range of temperatures, solvents, counterions, and lumophores have been explored. In addition, the ground-state equilibrium has been investigated through targeted theoretical calculations and experiments. The summation of these experiments provide unique insights into a class of novel exciplex-mediated proton-coupled charge-transfer reactions.
Adiabatic Proton-Coupled Charge-Transfer Reactions and Photochemistry of N, N-Dimethyl-3-arylpropan-1-ammonium Salts
Author: Trevor Safko
Publisher:
ISBN:
Category : Chemistry
Languages : en
Pages : 282
Book Description
The coupling of proton and electron transfers in concerted or sequential processes is of central importance to many biochemical and catalytic reactions. In this context, proton-coupled electron transfer reactions are typically described electrochemically, whereby the transfer of a proton is coordinated to a change in the oxidation state of the constituent donor/acceptor pairs. In the excited-state, intermolecular proton transfers are often facilitated through a redistribution of electron-density (charge-transfer) along the proton-transfer reaction coordinate without a corresponding change in the oxidation state of the donor/acceptor pair. Distinguishing charge-transfer from full electron-transfer reactions along the excited-state potential energy surface has received increased attention as advancements in engineering allow for the interrogation of the fastest molecular events. This dissertation seeks primarily to examine the confluence of charge-transfer, electron-transfer, and proton-transfer reactions which occur adiabatically in the excited-states of N, N-dimethyl-3-arylpropan-1-ammonium salts in solution. For these compounds, an excited-state intermolecular proton-transfer to the solvent is accompanied by intramolecular charge-transfer and the formation of either an emissive exciplex or a transient solvent-separated ion pair. The various electronic configurations have been interrogated through an array of spectroscopic techniques in order to more thoroughly understand the convergence of thermodynamic and kinetic factors affecting the proposed mechanism. In this regard, a range of temperatures, solvents, counterions, and lumophores have been explored. In addition, the ground-state equilibrium has been investigated through targeted theoretical calculations and experiments. The summation of these experiments provide unique insights into a class of novel exciplex-mediated proton-coupled charge-transfer reactions.
Publisher:
ISBN:
Category : Chemistry
Languages : en
Pages : 282
Book Description
The coupling of proton and electron transfers in concerted or sequential processes is of central importance to many biochemical and catalytic reactions. In this context, proton-coupled electron transfer reactions are typically described electrochemically, whereby the transfer of a proton is coordinated to a change in the oxidation state of the constituent donor/acceptor pairs. In the excited-state, intermolecular proton transfers are often facilitated through a redistribution of electron-density (charge-transfer) along the proton-transfer reaction coordinate without a corresponding change in the oxidation state of the donor/acceptor pair. Distinguishing charge-transfer from full electron-transfer reactions along the excited-state potential energy surface has received increased attention as advancements in engineering allow for the interrogation of the fastest molecular events. This dissertation seeks primarily to examine the confluence of charge-transfer, electron-transfer, and proton-transfer reactions which occur adiabatically in the excited-states of N, N-dimethyl-3-arylpropan-1-ammonium salts in solution. For these compounds, an excited-state intermolecular proton-transfer to the solvent is accompanied by intramolecular charge-transfer and the formation of either an emissive exciplex or a transient solvent-separated ion pair. The various electronic configurations have been interrogated through an array of spectroscopic techniques in order to more thoroughly understand the convergence of thermodynamic and kinetic factors affecting the proposed mechanism. In this regard, a range of temperatures, solvents, counterions, and lumophores have been explored. In addition, the ground-state equilibrium has been investigated through targeted theoretical calculations and experiments. The summation of these experiments provide unique insights into a class of novel exciplex-mediated proton-coupled charge-transfer reactions.
Photoinduced Electron Transfer: Photoinduced electron transfer reactions, organic substrates
Author: Marye Anne Fox
Publisher:
ISBN:
Category : Chemical reaction, Conditions and laws of
Languages : en
Pages : 784
Book Description
Publisher:
ISBN:
Category : Chemical reaction, Conditions and laws of
Languages : en
Pages : 784
Book Description
Amino Group Chemistry
Author: Alfredo Ricci
Publisher: John Wiley & Sons
ISBN: 352762127X
Category : Science
Languages : en
Pages : 408
Book Description
Here, probably the most important functional group in organic chemistry is discussed in one handy volume. The monograph covers its application -- from natural products to synthetic pharmaceuticals -- detailing complex syntheses using the amino group as templates and modern techniques focussing on the introduction of the amino group. A definitive must-have for every chemist.
Publisher: John Wiley & Sons
ISBN: 352762127X
Category : Science
Languages : en
Pages : 408
Book Description
Here, probably the most important functional group in organic chemistry is discussed in one handy volume. The monograph covers its application -- from natural products to synthetic pharmaceuticals -- detailing complex syntheses using the amino group as templates and modern techniques focussing on the introduction of the amino group. A definitive must-have for every chemist.
Practical Synthetic Organic Chemistry
Author: Stéphane Caron
Publisher: John Wiley & Sons
ISBN: 1119448859
Category : Science
Languages : de
Pages : 850
Book Description
This book is a hands-on guide for the organic chemist. Focusing on the most reliable and useful reactions, the chapter authors provide the information necessary for a chemist to strategically plan a synthesis, as well as repeat the procedures in the laboratory. Consolidates all the key advances/concepts in one book, covering the most important reactions in organic chemistry, including substitutions, additions, eliminations, rearrangements, oxidations, reductions Highlights the most important reactions, addressing basic principles, advantages/disadvantages of the methodology, mechanism, and techniques for achieving laboratory success Features new content on recent advances in CH activation, photoredox and electrochemistry, continuous chemistry, and application of biocatalysis in synthesis Revamps chapters to include new and additional examples of chemistry that have been demonstrated at a practical scale
Publisher: John Wiley & Sons
ISBN: 1119448859
Category : Science
Languages : de
Pages : 850
Book Description
This book is a hands-on guide for the organic chemist. Focusing on the most reliable and useful reactions, the chapter authors provide the information necessary for a chemist to strategically plan a synthesis, as well as repeat the procedures in the laboratory. Consolidates all the key advances/concepts in one book, covering the most important reactions in organic chemistry, including substitutions, additions, eliminations, rearrangements, oxidations, reductions Highlights the most important reactions, addressing basic principles, advantages/disadvantages of the methodology, mechanism, and techniques for achieving laboratory success Features new content on recent advances in CH activation, photoredox and electrochemistry, continuous chemistry, and application of biocatalysis in synthesis Revamps chapters to include new and additional examples of chemistry that have been demonstrated at a practical scale