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Definition and Emergence of Supramolecular

Chemistry
Jonathan W. Steed1 , Jerry L. Atwood2 , and Philip A. Gale3
1

Durham University, Durham, UK


University of Missouri, Columbia, MO, USA
3
University of Southampton, Southampton, UK
2

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

Adapted in part from Supramolecular Chemistry, J. W. Steed and


J. L. Atwood, Wiley: Chichester, 2nd Ed., 2009.

be a monatomic cation, a simple inorganic anion, an ion


pair, or a more sophisticated molecule such as a hormone,
pheromone, or neurotransmitter. More formally, the host is
defined as the molecular entity possessing convergent binding sites (e.g., Lewis basic donor atoms, hydrogen-bond
donors, etc.). The guest possesses divergent binding sites
(e.g., a spherical, Lewis acidic metal cation, or hydrogenbond-accepting halide anion). In turn, a binding site is
defined as a region of the host or guest capable of taking
part in a noncovalent interaction. The hostguest relationship has been defined by Donald Cram2 as follows:
Complexes are composed of two or more molecules or ions
held together in unique structural relationships by electrostatic forces other than those of full covalent bonds . . .
molecular complexes are usually held together by hydrogen bonding, by ion pairing, by -acid to -base interactions, by metal-to-ligand binding, by van der Waals attractive forces, by solvent reorganising, and by partially made
and broken covalent bonds (transition states). . .High structural organisation is usually produced only through multiple
binding sites. . . A highly structured molecular complex is
composed of at least one host and one guest component. . .
A hostguest relationship involves a complementary stereoelectronic arrangement of binding sites in host and guest. . .
The host component is defined as an organic molecule or
ion whose binding sites converge in the complex . . . The
guest component as any molecule or ion whose binding sites
diverge in the complex . . .

This description might well be generalized to remove


the word organic, since more recent work has revealed
a wealth of inorganic hosts, such as zeolites3 and
polyoxometallates,4 or mixed metalorganic coordination
compounds, such as metalorganic frameworks (MOFs)

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

Definition of traditional supramolecular hostguest chemistry according to Lehn.5

(see Zeolitelike MetalOrganic Frameworks (ZMOFs):


Design, Structure, and Properties, Supramolecular Materials Chemistry), which perform similar functions and may
be thought of under the same umbrella.

Supermolecule (complex):
Degree of order
Interactions between subunits
Symmetry of packing
Intermolecular interactions

EMERGENCE

The original supramolecular hostguest complexes


involve a host molecule that possesses an intrinsic molecular cavity into which the guest fits; hence, they are, in principle, stable in all forms of matter (solid, liquid/solution,
and the gas phase). The hostguest concept is much older
than the work by Pedersen6 on hosts for alkali metal ions
in the late 1960s that gave birth to modern supramolecular chemistry and can be dated back to the extensive body
of clathrate or solid-state inclusion chemistry. This field
begins with the twin descriptions of zeolites or boiling
stones discovered by Axel Cronstedt in 1756 and clathrate
hydrates or anomalous ice prepared by Joseph Priestley
in 1778. The evolution of this area is elucidated later in
this work by Bishop (see Synthetic Clathrate Systems,
Supramolecular Materials Chemistry) and forms much of
the early part of our subjective timeline of supramolecular
chemistry (Table 1).
Interspersed among these milestones is the parallel birth
of self-assembly as in the formation of self-assembled
monolayers first observed as the spreading of oil on water
by Benjamin Franklin in 1774, and the birth of nanochemistry (the 1818 recognition of the particle size-dependent
color of colloidal gold). We can also see the evolution of
crystal engineering from the early topochemical postulate
and molecular engineering of von Hippel in the 1960s to

the supramolecular synthon approach of Desiraju in 1995.


The years 1989 and 1995 mark milestones in the design
and synthesis of coordination polymer systems that have
brought about the explosion of porous MOF chemistry over
the past decade.
Biological receptorsubstrate supramolecular chemistry
and, by generalization, the whole of modern hostguest
chemistry has its roots in three core concepts:
1. The recognition by Paul Ehrlich in 1906 that molecules
do not act if they do not bind, Corpora non agunt nisi
fixata; in this way, Ehrlich introduced the concept of a
biological receptor.
2. The recognition in 1894 by Emil Fischer that binding must be selective, as part of the study of receptorsubstrate binding by enzymes. He described this
by a lock -and -key image of steric fit in which the guest

Substrate

(a)

Lock and key

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

Definition and emergence of supramolecular chemistry

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

Axel Cronstedt: description of boiling stone (zeolite)


Benjamin Franklin: spreading of oil on water
Joseph Priestly: anomalous ice
Sir Humphrey Davy: discovery of chlorine hydrate
Jeremias Benjamin Richters: particle size explanation for the color of drinkable gold; colloidal gold known since antiquity
(e.g., Lycurgus cup, fourth century AD)
Michael Faraday: formula of chlorine hydrate
C. Schafhautl: study of graphite intercalates
F. Wohler: -quinol H2 S clathrate
Villiers and Hebd: cyclodextrin inclusion compounds
Agnes Pockles: the first surface balance, leading to the development of the Langmuir trough and the LangmuirBlodgett
technique
Alfred Werner: coordination chemistry
Emil Fischer: lock-and-key concept
Paul Ehrlich: introduction of the concept of a receptor

K. L. Wolf: the term Ubermolek


ule is coined to describe organized entities arising from the association of coordinatively
saturated species (e.g., the acetic acid dimer)
Linus Pauling: hydrogen bonds are included in the groundbreaking book The Nature of the Chemical Bond
M. F. Bengen: urea channel inclusion compounds
H. M. Powell: X-ray crystal structures of -quinol inclusion compounds; the term clathrate is introduced to describe
compounds where one component is enclosed within the framework of another
Brown and Farthing: synthesis of [2.2]paracyclophane
Watson and Crick: structure of DNA
Dorothy Crowfoot Hodgkin: X-ray crystal structure of vitamin B12
Daniel Koshland: induced fit model
Donald Cram: attempted synthesis of cyclophane charge-transfer complexes with (NC)2 C=C(CN)2
N. F. Curtis: first Schiffs base macrocycle from acetone and ethylene diamine
Busch and Jager: Schiffs base macrocycles
Olga Kennard and J. D. Bernal: The Cambridge Structural Database
von Hippel: birth of crystal engineering
Charles Pedersen: crown ethers
Park and Simmons: Katapinand anion hosts
F. Toda: wheel and axel inclusion compound hosts
Jean-Marie Lehn: synthesis of the first cryptands
Jerry Atwood: liquid clathrates from alkyl aluminum salts
Ron Breslow: catalysis by cyclodextrins
G. M. J. Schmidt: topochemistry
Donald Cram: spherand hosts produced to test the importance of preorganization
Jean-Marie Lehn: introduction of the term supramolecular chemistry, defined as the chemistry of molecular assemblies and
of the intermolecular bond
Deliberate clathrate design strategies; hexahosts D. D. MacNicol and later in 1982 coordinatoclathrates E. Weber
Gokel and Okahara: development of the lariat ethers as a subclass of host
Vogtle and Weber: podand hosts and development of nomenclature
A. P. de Silva: fluorescent sensing of alkali metal ions by crown ether derivatives
Award of the Nobel prize for Chemistry to Donald J. Cram, Jean-Marie Lehn, and Charles J. Pedersen for their work in
supramolecular chemistry
G. M. Whitesides: self-assembled thiol monolayers on gold
R. Robson: 3D coordination polymers based on rod-like linkers
G. M. Whitesides: a chemical strategy for the synthesis of nanostructures
M. Brust: synthesis of thiol-stabilized gold nanoparticles
O. M. Yaghi: first MOF; key coordination polymer papers by M. J. Zaworotko and J. S. Moore
G. Desiraju: supramolecular synthon approach to crystal engineering
Atwood, Davies, MacNicol, and Vogtle: publication of Comprehensive Supramolecular Chemistry containing contributions
from many key groups and summarizing the development and state of the art
J. K. M. Sanders: the first example of a dynamic combinatorial chemistry system
Rowan and Nolte: helical supramolecular polymers from self-assembly
J. F. Stoddart: molecular electronics based on interlocked molecules
J. F. Stoddart: the first discrete Borromean-linked molecule, a landmark in topological synthesis

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.

Receptorsubstrate chemistry underwent a huge


paradigm shift in 1958 with Koshlands induced fit
model (Figure 2b), and these concepts have since permeated throughout biological and abiotic supramolecular
chemistry.
Supramolecular chemistry as we understand it today has
evolved to encompass not just host and guest chemistry
but also all aspects of self-assembly. It includes the design
and function of molecular devices and molecular assemblies, noncovalent polymers, and soft materials such as

Larger molecule
(Host)
Crystallization

Smaller molecule
(Guest)

Lattice inclusion hostguest complex or clathrate


(Solid-state only)

(a)

Covalent
synthesis

Small molecular
guest

Small molecules
Hostguest complex

Large host molecule


(b)

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

Definition and emergence of supramolecular chemistry


liquid crystals, informed nanoscale chemistry, and bottomup nanotechnology. In 2002, Lehn added a functional
definition: Supramolecular Chemistry aims at developing
highly complex chemical systems from components interacting by noncovalent intermolecular forces.7 Hence, the
current emphasis is on increasing complexity and hence
increasingly sophisticated functionality and on the information stored in molecular components that allows this
complexity to be achieved.
Modern supramolecular systems are beginning to display complex emergent properties based on the nonlinear
interactions between the molecular component parts. It is
clear that there are certain properties and features that
emerge according to the length scale on which a system
assembles, and indeed on which it is studied. Thus, the
way in which ostensibly easily understood molecular-level
supramolecular interactions scale up into the nanoworld
is not always predictable and represents the frontiers and
future of supramolecular science. As direct microscopic
imaging and manipulation on the multinanometer scale
become increasingly technologically feasible, it is increasingly possible to study the fascinating consequences of
chemical emergence the arising of novel and coherent
structures, patterns, and properties during the process of
self-organization in complex systems.8
Fundamentally, supramolecular chemistry concerns the
mutual interaction of molecules or molecular entities with
discrete properties. This interaction is usually of a noncovalent type (an intermolecular bond such as a hydrogen
bond, dipolar interaction, or -stacking). Key to many definitions of supramolecular chemistry is a sense of modularity. Supermolecules, in the broad sense, are aggregates
in which a number of components (of one or more type)
come together, either spontaneously or by design, to form a
larger entity with properties derived from those of its components. These aggregates can be of the hostguest type
in which one molecule encapsulates the other or they can
involve mutually complementary, or self-complementary,
components of similar size in which there is no host or
guest. We can thus trace the evolution of supramolecular
chemistry from the original solid-state clathrate paradigm
(Figure 3a), through the molecular hostguest paradigm
(Figure 3b) to the self-assembly paradigm (Figure 3c).
As it is currently practiced, supramolecular chemistry,
with its emphasis on the interactions between molecules,
underpins a very wide variety of chemistry and materials
science impinging on molecular hostguest chemistry,
solid-state hostguest chemistry, crystal engineering and
the understanding and control of the molecular solid state
(including crystal structure calculation), supramolecular

devices, self-assembly and self-organization, soft materials,


nanochemistry and nanotechnology, complex matter, and
biological chemistry. Dario Braga has summed up the
impact of supramolecular concepts in the following way9 :
The supramolecular perception of chemistry generated a
true paradigm shift: from the one focused on atoms and
bonds between atoms to the one focused on molecules and
bonds between molecules. In its burgeoning expansion the
supramolecular idea abated, logically, all traditional barriers between chemical subdivisions (organic, inorganic,
organometallic, biological) calling attention to the collective properties generated by the assembly of molecules and
to the relationship between such collective properties and
those of the individual component.

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