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Chemistry
Jonathan W. Steed1 , Jerry L. Atwood2 , and Philip A. Gale3
1
1 Introduction
2 Emergence
3 Conclusion
References
1
2
5
5
INTRODUCTION
Although the word supramolecular made an early appearance in Websters Dictionary in 1903, Supramolecular
chemistry in its modern sense was introduced only in 1978
by Lehn, who defined it as the . . .chemistry of molecular assemblies and of the intermolecular bond.1 Classic
explanations of supramolecular chemistry describe it as
chemistry beyond the molecule, the chemistry of the
noncovalent bond, and nonmolecular chemistry, or even
Lego chemistry. The early work in the field concerned the
formation of supermolecules comprising two components, a
host and a guest, which interact with one another in a noncovalent manner (Figure 1). The host is a large molecule or
aggregate such as an enzyme or synthetic cyclic compound
possessing a sizeable, central hole, or cavity. The guest may
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc002
Concepts
Molecular chemistry
Host
Supramolecular chemistry
Molecular
precursors
Specific characteristic,
function or properties:
Recognition
Catalysis
Transport
+
+
Covalent molecule:
Chemical nature
Shape
Redox properties
HOMOLUMO gap
Polarity
Vibration and rotation
Magnetism
Chirality
Figure 1
Guest
Supermolecule (complex):
Degree of order
Interactions between subunits
Symmetry of packing
Intermolecular interactions
EMERGENCE
Substrate
(a)
Enzyme
Complex
+
Induced fit
(b)
Figure 2 (a) Rigid lock and key and (b) induced fit models of
enzymesubstrate (and hence hostguest) binding.
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc002
Table 1 An illustrative timeline charting the development of supramolecular chemistry from its roots in solid-state inclusion
compounds, through the birth of macrocyclic hostguest chemistry in the 1960s to its modern incarnation in self-assembled materials
and nanoscale chemistry.
1756
1774
1778
1810
1818
1823
1841
1849
1891
1891
1893
1894
1906
1937
1939
1940
1945
1949
1953
1956
1958
1959
1961
1964
1965
1962
1967
1968
1968
1969
1969
1969
1971
1973
1978
1976
1979
1981
1986
1987
1989
1989
1991
1994
1995
1995
1996
1996
1998
1999
2004
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc002
3.
Concepts
has a geometric size or shape complementarity to the
receptor or host (Figure 2a). This concept laid the basis
for molecular recognition, the discrimination by a host
between a number of different guests.
The fact that selective binding must involve attraction
or mutual affinity between the host and guest. This
is, in effect, a generalization of Alfred Werners 1893
theory of coordination chemistry, in which metal ions
are coordinated by a regular polyhedron of ligands
binding by dative bonds.
Larger molecule
(Host)
Crystallization
Smaller molecule
(Guest)
(a)
Covalent
synthesis
Small molecular
guest
Small molecules
Hostguest complex
Covalent
synthesis
Small molecules
(c)
Spontaneous
Larger molecule
Self-assembled
aggregate
Figure 3 Key paradigms in supramolecular chemistry. (a) Solid-state clathrate paradigm, (b) molecular hostguest paradigm, and
(c) self-assembly paradigm.
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc002
CONCLUSION
It is clear that the molecular-level approach to understanding binding phenomena that gave rise to supramolecular
chemistry has found application in a vast array of phenomena and is to a great extent fueling the concepts and growth
of a vast swathe of chemically related science. For example,
future applications of supramolecular chemistry in biological systems may include new treatments for disease by the
inhibition of proteinprotein interactions or by the perturbation via synthetic channels or carriers of chemical and
potential gradients within cancer cells triggering apoptosis.
From molecules to supramolecular assemblies, to nanomaterials and complex molecular biosystems, the ensuing
chapters in these volumes capture in detail the backdrop
and current state of the art in all of these fields that are
driven or informed by supramolecular concepts.
REFERENCES
1. J.-M. Lehn, Angew. Chem. Int. Ed. Engl., 1988, 27, 89.
2. D. J. Cram, Angew. Chem. Int. Ed. Engl., 1986, 25, 1039.
3. R. Szostak, Molecular Sieves, Van Nostrand Reinhold, New
York, 1989.
4. A. Muller, E. Krickemeyer, J. Meyer, et al., Angew. Chem.
Int. Ed. Engl., 1995, 34, 2122.
5. J.-M. Lehn, Supramolecular Chemistry, 1st edn, Wiley-VCH
Verlag GmbH, Weinheim, 1995.
6. R. M. Izatt, Chem. Soc. Rev., 2007, 36, 143147.
7. J.-M. Lehn, Proc. Nal. Acad. Sci. U.S.A., 2002, 99, 4763.
8. J. Goldstein, Emergence: Complex. Organ., 1999, 1, 49.
9. D. Braga, Chem. Commun., 2003, 2751.
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc002