Proton-coupled electron transfer : from basic principles to small molecule activation

Proton-coupled electron transfer (PCET) is the basic mechanism for bioenergetic conversion. Hallmark examples of such reactivities include water oxidation which is coupled to photosynthesis and oxygen reduction which is coupled to ATP generation by respiration. These two complementary energy converstion schemes are intimately controlled by PCET in Nature. Despite the importance of PCET in such catalytic bond-making and bond-breaking reactions, the underlying mechanisms by which electron and proton transport couple to one another are not particularly not well understood. To address mechanistic issues surrounding the role of PCET in long range charge transport in biology and catalytic chemical transformations, we have undertaken a multifaceted investigation of PCET events at the molecular level. Two distinct lines of study have been embarked upon. The first revolves around the design, synthesis and photophysical interrogation of supramolecular D-[H+]-A PCET models. Such architectures are composed of two redox sites linked together in a lateral arrangement via a hydrogen-bonding interface.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2007

Author dc:creator

• Rosenthal, Joel, 1979-

Advisor dc:contributor.advisor

• Daniel G. Nocera.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/39736

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/39736