The Encapsulation Phenomenon: Synthesis, Reactivity and Applications of Caged Ions and Molecules

653 Pages·2016·125.109 MB·English

by  Yan Voloshin, Irina Belaya, Roland Krämer (auth.)

Yan Voloshin
Irina Belaya
Roland Krämer
The Encapsulation
Phenomenon
Synthesis, Reactivity and Applications of
Caged Ions and Molecules
The Encapsulation Phenomenon

Yan Voloshin (cid:129) I rina Belaya
Roland Krämer
The Encapsulation
Phenomenon
Synthesis, Reactivity
and Applications of Caged Ions
and Molecules
Yan Voloshin Roland Krämer
Nesmeyanov Institute of Organoelement Anorganisch Chemisches Institut
Compounds, Russian Academy Ruprecht-Karls-Univers. Heidelberg
of Sciences and Gubkin Russian State Heidelberg
University of Oil and Gas Germany
Moscow
Russia
Irina Belaya
Nesmeyanov Institute of Organoelement
Compounds, Russian Academy
of Sciences
Moscow
Russia
ISBN 978-3-319-27737-0 ISBN 978-3-319-27738-7 (eBook)
DOI 10.1007/978-3-319-27738-7
Library of Congress Control Number: 2016938266
© Springer International Publishing Switzerland 2016
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Y.Z.V. dedicates this book to his beloved son Sasha
and daughter Lisa

Pref ace

Nowadays, a separate realm of modern chemistry is populated by compounds
with encapsulated species. Those may be organic and inorganic, anions,
cations or neutral molecules that are almost completely isolated from external
factors (other ligands, solvents, etc.) by 3D caging (encapsulating) ligands to
give molecular and polymeric capsules. The caged species have unique phys-
icochemical properties responsible for specifi c reactivity and selectivity of
their binding and release. The resulting cage complexes may be used for rec-
ognition, separation, carrying, storage, and detection of various encapsulated
species in the fi eld of molecular and supramolecular devices and modern
materials, such as catalysts, carriers of therapeutically active compounds, and
many others.
Depending on the nature of chemical or supramolecular bonds between
precursors (ligand syntones, some of them are shown in i talic ) of the ligands
(shown in b old ), the cage complexes can be divided into three main classes:
covalent, supramolecular, and coordination capsules.
Covalent capsules (Chap. 2 ) include imine cages and their reduced deriva-
tives; amine, amide, and pyrrole encapsulating ligands; cryptophanes and
cryptands; and arene- and cavitand-based capsules. These subclasses refl ect
the nature of their caging ligands. The pioneering works of J.-M. Lehn,
D.J. Cram, and J. Nelson should be emphasized; further development in this
fi eld has been achieved by M. Mastalerz, A.P. Davis, A.I. Cooper, V. Amendola,
J.-P. Dutasta, F. Huang, K. Severin, and their coworkers.
S upramolecular capsules (Chap. 3 ) can be divided into two main sub-
classes: arene- and cavitand-based assemblies. J. Rebek Jr. and D.N. Reinhoudt
are pioneers in the fi eld of these “soft” encapsulating ligands and their cage
complexes. General experimental and theoretical (such as so-called “Rebek’s
rule”) approaches to the design, synthesis, and study of supramolecular cap-
sule have been also introduced by J. Rebek Jr., with a valuable input from
B.C. Gibb, D. Ajami, J. L. Atwood, D. Rudkevich, and A. Shivanyuk.
C oordination capsules (Chap. 4 ) , formed by coordination-driven self-
assembly of complimentary organic syntones containing donor groups with
appropriate metal ions, can be divided into three main subclasses depending
on the nature of their cage frameworks (4n- and 6n-capped capsules) and
coordination modes (bridging or cross-linking) of the metal ions. Pioneering
efforts in synthetic and physical chemistry of these capsules have been made
by M. Fujita and K.N. Raymond. Several new types of coordination capsules
have been also designed and prepared by J.R. Nitschke, R.W. Saalfrank,
vii
viii Preface
M.J. Hardie, M.D. Ward, K. Severin, G.H. Clever, P.D. Beer, M. Shionoya,
and their coworkers.
Continuous progress in the chemistry of these classes of compounds with
encapsulated species has been summarized in several reviews by J. Rebek Jr.
and coworkers [1–17] and, very recently, by M. Yoshizawa [18]. The coordina-
tion capsules have been nicely covered by M. Fujita [19–25], K.N. Raymond
[26–31], and others [32–40] and, more recently, by J.R. Nitschke [41–45],
G.H. Clever [46], and M. Shionoya [47]. In 2002, we published the book
Clathrochelates: Synthesis, Structure and Properties [48] that summarized
general concepts and features of the complexes with an encapsulated metal ion.
M ain developments in the design and chemistry of covalent capsules and
their practical applications as they appeared to date are reported in many
reviews [21, 34, 35, 48–65] and books [66–69] by J.-M. Lehn, K. Bowman–
James, V. Amendola, A.P. Davis, and others in 1988–2013 and, very recently,
by M. Mastalerz [70].
The aim of this book is to generalize the main progress in the design and
synthesis of capsules with various caged species (some of them also shown in
italic) that are important for their classifi cation, reactivity, and practical
applications recognized in 2014.
T he authors would like to thank Dr. Ekaterina Lebed and Dr. Yulia Nelubina
(INEOS RAS) for their valuable contribution in writing the book. We are also
much indebted to Prof. M. Fujita for fruitful suggestions and comments.
Moscow, Russia Yan Z. Voloshin
Moscow, Russia Irina G. Belaya
Heidelberg, Germany Roland Krämer
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