Table Of Content861
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
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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
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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
