Photoinduced Electron Transfer V PDF
Preview Photoinduced Electron Transfer V
861 scipoT in Current yrtsimehC Photoinduced Electron refsnarT V Editor: .J Mattay With contributions by A. Albini, R. A. Bissell, E. Fasani, .P K. Freeman, H. Q. N. Gunaratne, .S A. Hatlevig, .P L. M. Lynch, G. E. M. Maguire, E Maslak, C. E McCoy, M. Mella, G. Pandey, K. R. A. S. Sandanayake, A.P. de Silva, .P-.J Soumillion htiW 33 serugiF dna 11 selbaT galreV-regnirpS Berlin Heidelberg kroYweN London Paris oykoT Hong Kong Barcelona tsepaduB This series presents critical reviews of the present position and future trends in modern chemical research. It is addressed to all research and industrial chemists who wish to keep abreast of advances in their subject. As a rule, contributions are specially commissioned. The editors and publishers will, however, always be pleased to receive suggestions and supplementary information. Papers are accepted for "Topics in Current Chemistry" in English. ISBN 3-540-56746-1 Springer-Verlag Berlin Heidelberg New York ISBN 0-387-56746-1 Springer-Verlag New York Berlin Heidelberg Library of Congress Catalog Card Number 226446-47 This work si subject to copyright. llA rights are reserved, whether the whole or part of the material is concerned, yllacificeps the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof si permitted only under the provisions of the German Copyright Law of September ,9 ,5691 in its current version, and permission for use must always be obtained from Springer-Vedag. Violations are liable for prosecution under the German Copyright Law. © Springer-Verlag Berlin Heidelberg 3991 Printed in Germany The use of general descriptive names, registered names, trademarks, etc. ni this publication does not imply, even in the absence of a cificeps statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Macmillan India Ltd., 52-erolagnaB Printing: Saladruck, Berlin, :gnidniB Liideritz & Bauer, nilreB 5-0203/15 4 3 2 1 0 - Printed on acid-free paper Preface to the Series on Photoinduced Electron Transfer The exchange of an electron from a donor molecule to an acceptor molecule belongs to the most fundamental processes in artificial and natural systems, although, at the primary stage, bonds are neither broken nor formed. However, the transfer of an electron determines the chemical fate of the molecular entities to a great extent. Nature has made use of this principle since the early beginnings of life by converting light energy into chemical energy via charge separation. In recent years man has learnt, e.g. from X- ray analyses performed by Huber, Michel and Deisenhofer, how elaborately the molecular entities are constructed within the supermolecular framework of proteins. The light energy is trans- ferred along cascades of donor and acceptor substrates in ordert o prevent back electron transfer as an energy wasting step and chemical changes are thus induced in the desired manner. Today we are still far away from a complete understanding of light-driven electron transfer processes in natural systems. It is not without reason that the Pimentel Report emphasizes the necessity of future efforts in this since field, to understanda nd "to replicate photosynthesis in the laboratory would clearly be a major triumph with dramatic implications". Despite the fact that we are at the very beginning of knowledge about these funda- mental natural processes, we have made much progress in under- standing electron transfer reactions in "simple" molecular sys- tems. For example most recently a unified view of organic and inorganic reaction mechanisms has been discussed by Kochi. In this context photochemistry plays a crucial role not only for the reasons mentioned above, but also as a tool to achieve electron transfer reactions. The literature contains a host of examples, inorganic as well as organic, homogeneous as well as heterogen- eous. Not surprisingly, most of them were published within the last decade, although early examples have been known since the beginning of photochemistry (cf. Roth's article in .)651.1oV A reason is certainly the rapid development of analytical methods, Preface which makes possible the study of chemical processes at very short time ranges. Eberson in his monograph, printed by this publishing company two years ago, nicely pointed out that "electron transfer theories come in cycles". Though electron transfer has been known to inorganic chemists for a relatively long time, organic chc 'nist have still to make up for missing concepts Eberson). (cf. A major challenge for research in future, the "control of chemical reactions" as stated by the Pimentel Report, can be approached by various methods; light-driven processes are am- ong the most important ones. Without interaction of the diverse scientific disciplines, recent progress in photochemistry, as well as future developments would scarcely be possible. This is parti- cularly true fotrh e study of electront ransfer processes. Herein lies a challenge for science and economy and the special facsination of this topic - at least for the guest editor. The scope of photochemistry and the knowledge about the fundamentals of photoinduced electron transfer reactions have tremendously broadened within the last decade, as have their applications. Therefore I deeply appreciate that the Springer- Verlag has shown interest in this important development and is introducing a series of volumes on new trends in this field. It is clear that not all aspects of this rapidly developing topic can be exhaustively compiled. I have therefore tried to select some papers which most representatively reflect the current state of research. Several important contributions might be considered missing by those readers who are currently involved in this field, however, these scientists are referred to other monographs and periodical review series which have been published recently. These volumes are meant to give an impression of this newly discovered reaction type, its potential and on the other hand to complement other series. The guest editor deeply appreciates that well-known experts have decided to contribute to this series. Their effort was sub- stantial and I am thankful to all of them. Finally, I wish to express my appreciation to Dr. Stumpe and his coworkers at the Sprin- ger-Verlag for helping me with all the problems which arose during the process of bringing the manuscript together. Mtinster, December 9891 Jochen Mattay VIII Preface to Volume V Included in this volume are six articles devoted to a process which is basic not only in chemistry, but in biology and physics. The intent is to provide a critical review of some topics in photo- induced electron transfer (PET) in order to complement existing works. All articles are concerned with experimental and theoret- ical aspects of PET in organic chemistry. The interdisciplinary character of PET is already reflected in the preceding volumes of this series as will be so in the following volumes for electron transfer in general. PET V starts with a survey of fragmentation reactions which, as one of the most important events after the initial transfer of an electron, competes with back-electron transfer. The factors con- trolling this latter process as well as the thermodynamics, kinetics and the stereochemistry of the fragmentations are comprehen- sively discussed. The second article deals with dehydrohalogen- ation of polyhalocompounds emphasizing both the nature of excimers in the phototransformation and the nature of exciplexes formed in the presence of electron transfer reagents. The impact photochemistry has on toxic waste disposal concludes this chap- ter. The special features of organic anions in PET-reactions are critically discussed in the following article. Despite the advantages such as the increased electron donating capacity, the reactivity is strongly influenced by the experimental conditions. NRS 1 reac- tions, alkylations of carbanions and reductions initiated by oxy- anions are discussed in detail as well as the quenching of excited states by anions in their ground state. Aromatic compounds have been used as electron acceptors and electron donors in PET-processes since the early beginnings of photochemistry. Chapter 4 of this volume is devoted to this still fascinating area mainly from the synthetic point of view. Special emphasis is given to recombination reactions of radical ions, electrophilic, nucleophilic and radicalic additions. The following article extends this topic to recent advances of PET in organic ecaferP to emuloV v synthesis. Several new reactions are discussed covering photo- sensitized electron transfer processes and donor-acceptor reac- tions. The final chapter turns to new developments in the field of fluorescent PET sensors. In this article the design of an efficient model system containing both a selective receptor and a fluoro- phore is vividly described. A variety of sensor systems with an eventually high potential for application is discussed. The guest editor deeply acknowledges that colleagues well- known as expertsf or years havea greed to contribute to this series. Their effort was substantial just as the support of Dr. Stumpe and his coworkers at Springer-Verlag in preparing the volume. Mfinster, May 1993 Jochen Mattay Attention all "Topics in Current Chemistry" readers: A file with the complete volume indexes Vols. 22 (1972) through 167 (1993) in delimited ASCII format is available for downloading at no charge from the Springer EARN mailbox. Delimited ASCII format can be imported into most databanks. The file has been compressed using the popular shareware pro- gram "PKZIP" (Trademark of PKware Inc., PKZIP is available from most BBS and shareware distributors). This file is distributed without any expressed or implied warranty. To receive this file send an e-mail message to: SVSERV @ DHDSPRI6.BITNET. The message must be: "GET/CHEMISTRY/TCC_CONT.ZIP". SVSERV is an automatic data distribution system. It responds to your message. The following commands are available: HELP returns a detailed instruction set for the use of SVSERV, DIR )eman( returns a list of files available in the directory "name", INDEX (name) same as "DIR", CD (name) changes to directory "name", SEND ) (filename invokes a message with the file "file- name", GET emanelifxr ) same as "SEND". For more information send a message to: INTERNET: STUMPE@ SPINT. COMPUSERVE. COM Table of Contents Fragmentations by Photoinduced Electron Transfer. Fundamentals and Practical Aspects P. Maslak ............................. The Photochemistry of Polyhalocompounds, Dehalogenation by Photoinduced Electron Transfer, New Methods of Toxic Waste Disposal P.K. Freeman, S.A. Hatlevig ................... 47 Photoinduced Electron Transfer Employing Organic Anions J.-P. Soumillion .......................... 93 PET-Reactions of Aromatic Compounds A. Albini, E. Fasani, M. Mella ................ 143 Photoinduced Electron Transfer (PET) in Organic Synthesis G. Pandey ............................ 175 Fluorescent PET (Photoinduced Electron Transfer) Sensors R.A. Bissell, A.P. de Silva, H.Q.N. Gunaratne, P.UM. Lynch, G.E.M. Maguire, C.P. McCoy, K.R.A.S. Sandanayake ..................... 223 Author Index Volumes 151-168 ................ 265 Table of Contents of Volume 156 A Brief History of Photoinduced Electron Transfer dna Related Reactions H.D. Roth Fundamental Concepts of Photoinduced Electron Transfer G.J. Kavarnos Photoinduced Electron Transfer (PET) Bond Cleavage Reactions F.D. Saeva Photoinduced Electron Transfer of Carbanions and Carbocations E. Krogh and P. Wan Photoinduced Electron Transfer Oxygenations L. Lopez Photoinduced Electron Transfer Polymerization H.J. Timpe Electron Transfer Processes in Imaging D.F. Eaton Table of Contents of Volume 158 Photochemistry of Transition Metal Complexes decudnI yb Transfer Charge Outer-Sphere Excitation .A Vogler and H. Kunkely Metal Complexes as Light Absorption and Light Emission Sensitizers .V Balzani, F. Barigelletti and L. De Cola Electron Photoinduced dna Energy Transfer ni Polynuclear Complexes F. Scandola, M.T. Indelli, C. Chiorboli and C.A. Bignozzi Photoinduced Electron Transfer in Ion Pairs R. Billing, D. Rehorek and H. Hennig
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