Supramolecular Photochemistry: Controlling Photochemical Processes

629 Pages·2011·58.97 MB·English

SUPRAMOLECULAR
PHOTOCHEMISTRY
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SUPRAMOLECULAR
PHOTOCHEMISTRY
Controlling Photochemical Processes
EDITED BY
V. RAMAMURTHY
YOSHIHISA INOUE
A JOHN WILEY & SONS, INC., PUBLICATION
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Copyright © 2011 by John Wiley & Sons, Inc. All rights reserved
Published by John Wiley & Sons, Inc., Hoboken, New Jersey
Published simultaneously in Canada
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Library of Congress Cataloging-in-Publication Data
Supramolecular photochemistry : controlling photochemical processes / edited by
V. Ramamurthy, Yoshihisa Inoue.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-470-23053-4 (hardback)
1. Photochemistry. 2. Supramolecular chemistry. I. Ramamurthy, V. II. Inoue, Yoshihisa,
1949-
QD708.2.S87 2011
541'.226–dc22
2011010605
Printed in Singapore
obook ISBN: 978-1-118-09530-0
ePDF ISBN: 978-1-118-09527-0
ePub ISBN: 978-1-118-09529-4
10 9 8 7 6 5 4 3 2 1
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CONTENTS
Preface vii
Contributors xi
1 Dynamics of Guest Binding to Supramolecular Assemblies 1
Cornelia Bohne
2 Templating Photoreactions in Solution 53
Dario M. Bassani
3 Complexation of Fluorescent Dyes by Macrocyclic Hosts 87
Roy N. Dsouza, Uwe Pischel, and Werner M. Nau
4 Supramolecular Photochirogenesis 115
Cheng Yang and Yoshihisa Inoue
5 Real-Time Crystallography of Photoinduced Processes in
Supramolecular Framework Solids 155
Philip Coppens and Shao-Liang Zheng
6 Bimolecular Photoreactions in the Crystalline State 175
Arunkumar Natarajan and Balakrishna R. Bhogala
7 Structural Aspects and Templation of Photochemistry in
Solid-State Supramolecular Systems 229
Menahem Kaftory
8 Photochromism of Multicomponent Diarylethene Crystals 267
Masakazu Morimoto and Masahiro Irie
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vi CONTENTS
9 Manipulation of Energy Transfer Processes Within the
Channels of L-Zeolite 285
Gion Calzaferri and André Devaux
10 Controlling Photoreactions Through Noncovalent
Interactions Within Zeolite Nanocages 389
V. Ramamurthy and Jayaraman Sivaguru
11 Photochemical and Photophysical Studies of and
in Bulk Polymers 443
Shibu Abraham and Richard G. Weiss
12 Delocalization and Migration of Excitation Energy and
Charge in Supramolecular Systems 517
Mamoru Fujitsuka and Tetsuro Majima
13 Supramolecular Effects on Mechanisms of Photoisomerization:
Hula Twist, Bicycle Pedal, and One-Bond-Flip 547
Robert S.H. Liu, Lan-Ying Yang, Yao-Peng Zhao,
Akira Kawanabe, and Hideki Kandori
14 Protein-Controlled Ultrafast Photoisomerization in
Rhodopsin and Bacteriorhodopsin 571
Hideki Kandori
Index 597
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PREFACE
Ancient civilizations recognized the importance of light for the maintenance
and sustenance of life on earth. As pointed out in ancient Indian scriptures,
“ The rising sun is the giver of energy, heat, all powers, happiness and prosper-
ity. ” The sun, the ultimate source of light that provides the energy that drives
life, has been an object of worship by various civilizations since antiquity.
However, orderly investigations of the connection between the absorption of
light by matter and its chemical and physical consequences were not reported
in the scientifi c literature until about the turn of the last century, when sys-
tematic efforts revealed that exposure of matter to sunlight led to a rich range
of transformations that are now termed p hotochemical reactions .
During the 1930s, gas - phase photochemistry was a popular area of study. In
the early 1940s, the theoretical concept of the “ triplet state ” of organic mol-
ecules was confi rmed with striking experimental evidence. The “ rules ” of the
photophysics of organic molecules were established by 1950, and correlations
were made between the spectroscopic properties of molecules and the orbital
confi gurations of electronically excited states. The 1960s and 1970s marked a
period when many new photoreactions were discovered, and the mechanisms
of these reactions were investigated with a cluster of powerful new spectro-
scopic techniques and theories. During this period, the power of mechanistic
investigations was demonstrated and the fi eld of molecular photochemistry
gained the status of a truly new and emerging discipline. It was only in the
1980, that photochemistry became an integral part of organic, inorganic and
biological chemistry. This development led photochemists to import concepts
from other disciplines and take the fi eld to a next level that is now called
“ Supramolecular Photochemistry. ”
vii
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viii PREFACE
Inspiration from and aspiration to mimic biological systems have been a
driving force for the advancement of supramolecular photochemistry. Tailoring
and tuning molecules have been one of the main goals of researchers exploring
this topic. “ Control ” has been a key element in most of the discoveries in this
fi eld. Twenty years ago one of us (VR) edited a monograph titled P hotochemistry
in Organized and Constrained Media that set the trend that was to come. In
the Foreword, George S. Hammond wrote, “ Study and exploitation of photo-
chemistry in organized media is a fi eld, if not in its infancy, barely past ado-
lescence. ” Since then, the fi eld of photochemistry has attracted a large number
of new researchers and has become more relevant in solving pressing current
problems related to sustainability, energy, and the environment. Its future role
in harnessing solar energy and developing environmentally friendly synthetic
methodologies cannot be overemphasized. In addition, during the last three
decades, photochemistry has found its way into a number of industrial and
medicinal applications; lithography and photodynamic therapy are just two
examples. There is no doubt that “ photochemistry with control ” will lead to
even more important useful outcomes in the future.
This book, with 14 chapters contributed by 28 chemists, covers both solu-
tion - and solid - state supramolecular assemblies as well as photophysics and
photochemistry of molecules that are integrated into the supramolecular
assembly. Reaction media discussed include crystals, zeolites, polymers, organic
glass, and organic host - guest assemblies in the solid state and in solution, as
well as within biological matrices. A comprehensive survey of “ supramolecular
photochemistry ” (photoreactions with control) contributed by experts in the
fi eld is expected to be of great value to students, teachers, and researchers. This
book can serve as a source of reference and as supplementary book in photo-
chemistry courses.
The book begins with a chapter by C. Bohne in which the author summa-
rizes various techniques that are used in probing the dynamics of supramo-
lecular assemblies. The author elegantly illustrates the power of these
techniques with examples chosen from micelles, cyclodextrins, and DNA. In
the second chapter D. Bassani critically evaluates the various strategies avail-
able to obtain selectivity in photocycloaddition reactions in solution. This
chapter also includes a summary of other photoreactions in which templation
has played a key role. Recently, cucurbiturils have been extensively explored
as a host in photochemical and photophysical studies. These studies have also
brought to forefront the potential of other hosts such as cyclodextrins, calix-
arenes, and other cavitands. In Chapter 3 , W. Nau, R. N. Dsouza, and U. Pischel
have highlighted the value of these hosts in photophysical studies and in sensor
applications. Chiral chemistry has been one of the passions of the editors of
this volume. In Chapter 4 , Y. Inoue and C. Yang review the advances in the
fi eld of supramolecular chiral photochemistry. The chapter includes studies in
zeolites, cyclodextrins, and proteins, and with organic chiral templates.
Chapters 5 to 8 deal with photochemical studies in crystals. Each one
emphasizes different aspects of solid - state photochemistry. Chapter 5 by
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PREFACE ix
P. Coppens and S. L. Zheng emphasizes the need to bring in a new technique
(time - resolved crystallography) to gain an in - depth understanding of
photoreactions in the crystalline state. Challenges are many, yet this may be
one of the few options we currently have to get an insight into what happens
in pico - , and nano - second time scales when molecules are excited in the crys-
talline state. Photodimerization in solid state continues to draw the attention
of chemists with both crystallographic and photochemical inclinations.
Photodimerization provides valuable examples that could be subject to deeper
investigation using more sophisticated modern and yet - to - be discovered
techniques. With that in mind A. Natarajan and B. R. Bhogala have summa-
rized what is known in the fi eld of photodimerization for over fi ve decades
in Chapter 6 . Since very early studies on urea - inclusion complexes, photo-
chemical studies of host - guest chemistry in the solid state (also known as
inclusion chemistry or clathrate chemistry ) have made steady progress. The
diverse literature on host - guest solid - state photochemistry has been beauti-
fully summarized by M. Kaftory, who himself has made pioneering contribu-
tions to this topic (Chapter 7 ). In the next chapter (Chapter 8 ), M. Irie and
M. Morimoto have summarized their work on the photochromism of diaryl-
ethylene crystals. This is one of the few photoreactions that has shown poten-
tial commercial value. If any device based on this reaction ever reaches the
commercial market, the public may begin appreciating the value of solid - state
photochemistry.
The next two chapters (Chapters 9 and 10 ) deal with the photochemistry
and photophysics of organic molecules included within zeolites. G. Calzaferri
has been a pioneer in exploring the highly ordered structure of zeolites to
channel light and electrons in an organized manner between molecules. In
Chapter 9 , he and A. Devaux have provided a detailed review of photophysics
of molecules included within zeolite L. This chapter is a must - read for anyone
wishing to explore zeolites in the context of solar energy capture. Chapter 10
by Ramamurthy and Sivaguru summarizes their contributions to the use of
zeolites to carry out selective photochemistry and photophysics. The authors
emphasize the value of zeolite cations in controlling excited - state chemistry
including chiral induction.
In addition to their widespread use in various commercial applications,
polymers are also used as a supramolecular matrix to carry out photochemical
and photophysical studies of doped organic molecules. R. G. Weiss and
S. Abraham provide an exhaustive and critical survey of this fi eld in Chapter
11 . All aspects of the excited - state chemistry of molecules included in poly-
mers have been covered. This chapter is not about photochemistry of polymers
(a topic covered by a number of books), but rather, it describes how the pho-
tochemistry within polymers is unique and how concepts presented here are
likely to lead to useful applications. In Chapter 12 , T. Majima and M. Fujitsuka
highlight the value of biopolymers as matrices for photoreactions. This chapter
focuses on the use of ultra - fast time - resolved techniques to probe charge and
energy migration in organized assemblies.
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x PREFACE
In Chapter 13 , R. S. H. Liu and co - authors illustrate how the mechanism of
a simple photoprocess such as c is - trans isomerization could change when
molecules are confi ned in matrices such as organic glass. While most investiga-
tors have focused their studies on discovering new reactions and controlling
excited - state chemistry, R. S. H. Liu, the proponent of the “ hula - twist, ” dem-
onstrates that the mechanism of known photoreactions could change within
supramolecular assemblies. In his elegant presentation, he argues how the
“ hula - twist ” can be important in crystals, proteins, and so on. The fi nal chapter
(Chapter 14 ) by H. Kandori is an important one for those of us who are
inspired to undertake supramolecular photochemistry in the laboratory. He
demonstrates that the best, most effi cient, rapid, and highly selective supra-
molecular photoprocess occurs in the human eye. A detailed presentation of
what is known on ultrafast photoisomerization of retinal that resides in a
protein pocket is an ideal example of the value of photochemistry research.
We hope that it motivates young investigators to undertake research on
“ supramolecular photochemistry ” in general.
We are grateful to authors for their patience and cooperation during the
entire process of production of this monograph. We are proud to have con-
vinced pioneers in the fi eld to contribute chapters to this volume. While we
recognize that color fi gures would have enhanced the quality of the topics,
due to cost control needs only black and white fi gures are included in the
text. However, readers are encouraged to view several color fi gures free
of charge at the Wiley ftp site: ftp://ftp.wiley.com/public/sci_tech_med/
supramolecular_photochemistry.
VR is grateful to the U.S. National Science Foundation for supporting his
research that has allowed him to keep his interest focused on this topic. YI
thanks the Japan Science and Technology Agency and Japan Society for the
Promotion of Science for their generous support of his research projects on
“ photochirogenesis ” in molecular, supramolecular, and biomolecular regimes.
VR and YI thank their former and present students and colleagues for their
devotion and collaboration. They also thank Ms. Anita Lekhwani, Senior
Commissioning Editor, Wiley - Blackwell for encouraging us to undertake this
project and for her perseverance despite the slow progress of the project. VR,
especially, has enjoyed the collaboration with Anita on various book projects
for over a period of 15 years. And most importantly, the editing of this book
would not have been possible without the understanding, patience, support,
and encouragement of our wives Rajee (VR) and Masako (YI).
V. R amamurthy
Y oshihisa I noue
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CONTRIBUTORS
Shibu Abraham, Department of Chemistry, Georgetown University,
Washington, DC 20057 - 1227
Dario M. Bassani, Institut des Sciences Mol é culaires, CNRS UMR 5255,
Universit é Bordeaux 1, 351 Cours de la Lib é ration, F - 33405 Talence,
France
Balakrishna R. Bhogala, Department of Chemistry, University of Miami,
Coral Gables, FL 33124
Cornelia Bohne, Department of Chemistry, University of Victoria, PO Box
3065, Victoria, BC, Canada V8W
Gion Calzaferri, Department of Chemistry and Biochemistry, University of
Bern, Freiestrasse 3, CH - 3012 Bern, Switzerland
Philip Coppens, Chemistry Department, University at Buffalo, State
University of New York, Buffalo, NY 14221
Andr é Devaux, Physikalisches Institut, Westf ä lische Wilhelms - Universit ä t
M ü nster, Mendelstr. 7, D - 48149 M ü nster, Germany
Roy N. Dsouza, School of Engineering and Science, Jacobs University Bremen,
Campus Ring 1, D - 28759 Bremen, Germany
Mamoru Fujitsuka, The Institute of Scientifi c and Industrial Research
(SANKEN), Osaka University, Mihogaoka 8 - 1, Ibaraki, Osaka, 567 - 0047,
Japan
Yoshihisa Inoue, Department of Applied Chemistry, Osaka University, 2 - 1
Yamada - oka, Suita 565 - 0871, Japan
xxii
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