Supramolecular

Chemistry
Supramolecular Chemistry By JW Steed, 2000
Concept of Supramolecular Chemistry By DR Turner, 2007
Macromolecular Chemistry: New Research By V Gartner, 2013

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 J.-M. Lehn

Supramolecular chemistry may be defined

as “chemistry beyond the molecule”,
bearing on the organized entities of higher
complexity that are resulted from the
association of two or more chemical
species held together by intermolecular
forces.

Supramolecular systems are the selforganized entities that are

resulted from the association of two or more molecules held
together by intermolecular forces (noncovalent bonds).

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What is Supramolecular Chemistry?

MOLECULAR CHEMISTRY – covalent bonds formation

SUPRAMOLECULAR CHEMISTRY – “non-covalent bond”
formation
J. M. Lehn:

„Supramolecular chemistry is the chemistry of the intermolecular

bond, covering the structures and functions of the entities formed
by the association of two or more chemical species“

F. Vögtle:

„In contrast to molecular chemistry, which is predominantly

based upon the covalent bonding of atoms, supramolecular
chemistry is based upon intermolecular interactions, i.e. on the
association of two or more building blocks, which are held
together by intermolecular bond”
 Nature of the intermolecular forces

Covalent bond 200-400 kJ/mol

Ion-ion interaction

Ion-dipole interaction 50-200 kJ/mol

Dipole-dipole interaction 5-50 kJ/mol

Hydrogen bond 4-120 kJ/mol

Cation –n(π) interaction 5-80 kJ/mol

π-π interaction 0-50 kJ/mol

Van-der-Waals interaction (<5 kJ/mol)

Hydrophobic effects 2-20 kJ/mol

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 The hierarchy of structural organization of matter

Atoms a b c

Molecules A(a-a) B(a-b) C(b-c)

covalent bonds
Supramolecular A ….. A A …… B
Supermolecules
systems A ……B ….. C Supramolecular
C ….. A assemblies
non-covalent bonds
(intermolecular)
Biological Community of mutually dependent
functionally different
systems supramolecular systems 5
Nature of Supramolecular Interactions

Bond Energies and lengths:

C-O bond 340kJ / mol 1.43Å
C-C bond 360kJ / mol 1.53Å
C-H bond 430kJ / mol 1.11Å
C=C bond 600kJ / mol 1.33Å
C=O bond 690kJ / mol 1.21Å

Compared to most non-covalent interactions these are:

• Very high energies

• Very short distances
• Highly dependant on orientation
 Types of Intermolecular Forces (IMF)
--- Should actually be called Interparticulate Forces
(molecules, ions, and/or atoms)
• Ion - ion forces
• Ion-dipole forces
• Dipole-dipole forces
• Dispersion Forces
• Hydrogen Bonds

Ion - ion forces: (lattice energy-ionic compound)

• Force depends on the charge on the ions and the

distance separating the ions
 Kinetic-Molecular Description
Intermolecular forces are attractive forces between molecules
Intramolecular forces hold atoms together in a molecule.
(covalent bond)

Intermolecular vs Intramolecular
• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)

Generally, intermolecular forces are much weaker than

intramolecular forces.(only about 15% as strong)
 Nature of Supramolecular Interactions
Ion - Ion Interactions

Can be a very strong bond - even stronger than covalent bonds in

somecases.
Can be an attractive or a repulsive force.
Non-directional force
Long range (1/r)
Highly dependant on the dielectric constant of the medium
Energy = (k * z1 * z2 * e2) / (e * r12)

k = 1 / 4πeo= Coulomb constant = 9*109Nm2/C2

e = elementary charge = 1.6*10-19C
e0 = dielectric constant
r12 = distance between the objects
The energy of an ion-ion interaction only falls of at a rate
proportional to 1 / r. Therefore these are very long range forces.
Na-Lattice figure
 Ion-Dipole Interaction

Energy = -(k * Q * u * cosq / e * r2)

u = q * l (dipole moment)
l = length of the dipole
q = partial charge on dipole
r = distance from charge to center of dipole
Q = charge on ion

Directional forces
Can be attractive or repulsive
Medium range (1/r2)
Significantly weaker then ion-ion interactions
 Intermolecular Forces

1. Ion-Dipole Forces

Attractive forces between an ion and a polar molecule

Example: ions in solution
Ion-Dipole Interaction
The strength of the interaction depends on the charge and
size of the ion and on the magnitude of the dipole moment
and size of the molecule.

Water molecules

Higher charge, smaller size strong interaction

 Intermolecular Forces

2. Dipole-Dipole Forces (permanent dipole moment)

Attractive forces between polar molecules

Orientation of Polar Molecules in a Solid

3. Temporary dipoles (Dispersion forces)

What attractive force occurs in nonpolar substances?

Attractive forces that arise as a result of temporary
dipoles induced in atoms or molecules

– Ion induced
– Dipole induced
– Instantaneous dipole

ion-induced dipole interaction

The electron distribution of atom is distorted
by the force exerted by the ions or polar
molecules.

dipole-induced dipole interaction

The likelihood of a dipole moment being induced depends not only
on the charge of the ion or the strength of the dipole but also on
the polarizability of the atom or molecules.

Polarizability is the ease with which the electron distribution

in the atom or molecule can be distorted.
Polarizability increases with:
• greater number of electrons
• more diffuse electron cloud

Dispersion forces usually increase

with molar mass (more electrons),
or size of the atom.

Melting point increases as

the number of electrons in
the molecule increase.
London Dispersion Force (Dispersion force)
Polarizability allows gases containing atoms or nonpolar
molecules (e.g.He,N2) to condense.

At any instant it is likely that the atom has a dipole moment

created by a specific positions of electrons. This dipole moment
is called instantaneous dipole.
Induced dipoles interacting with each other. This type of
interaction produces dispersion forces, which arise as a result of
temporary dipoles induced in atoms or molecules, is
responsible for the condensation of nonpolar gases.
**Dispersion force exists between all species.
 What type(s) of intermolecular forces exist between each of
the following molecules?

HBr
HBr is a polar molecule: dipole-dipole forces. There are
also dispersion forces between HBr molecules.

CH4
CH4 is nonpolar: dispersion forces.

S
SO2
SO2 is a polar molecule: dipole-dipole forces. There are
also dispersion forces between SO2 molecules.
4. Hydrogen Bond

The hydrogen bond is a special dipole-dipole interaction

between the hydrogen atom in a polar N-H, O-H, or F-H bond
and an electronegative O, N, or F atom.

A H…B or A H…A
A & B are N, O, or F
Hydrogen Bonds:

• Strength of H bonds: up to 40 kJ/mol

• Lots of H bonds = strong
• compare with strength of typical covalent bonds:
250 kJ/mole)
 1 – SYNTHETIC SUPRAMOLECULAR SYSTEMS
Investigation of supramolecular systems
of different architectures with different functions created
on the base of synthetic components

2 – NATURAL SUPRAMOLECULAR SYSTEMS

Investigation of architectures and functions of supramolecular
systems and their components separated from biological
objects

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Examples

The ultimate supramolecular

material?

Held together by many specific

hydrogen bonds, π-π stacking, etc.
Encodes gigabytes of data
Can Self-Replicate
Built-in Error Correction
Information Storage
Is the basis of life
DOUBLE SPIRALS

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Tobacco Mosaic Virus (TMV)
SELF-ORGANIZATION
Strip
H H H
O N O O N O O N O
H H H H
N N N N N N N N
H H H H H H
O N N O N N O
H H H H
N N N N N N
H H H H
Rosette
H
O N O

H H H H
N N N N
H H

N N O N N

H H H H
N N N N N N

H H H H
H H
O N O O N O
H H
N N N N N
H H H H
O N N O
H H
N N N 27
H H
 Biological systems are result of self-organization
of supramolecular systems

Supramolecular systems are result of self-organization

of molecules

Molecules are result of self-organization of atoms

Atoms are result of self-organization of elementary

particles

Self-organization is spontaneous formation of definite

ordered systems
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МEMBRANE WORLD supramolecular

RNA WORLD supramolecular

POLYPEPTIDE WORLD supramolecular

ENZYME WORLD supramolecular

SUPRAMOLECULAR WORLD

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 HYDROGEN BINDING OF NUCLEOTIDE BASES

Chemical Adenine Thymine

informatics

Information storage on
Guanine Cytosine
molecular level
but
Information readout on
supramolecular level

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 DNA DOUBLE SPIRAL

H
N
H
ADENINE
O N C C N
HC
C C
O P O N N H

O O
GUANINE
O

O N H
N

N H
O P O N N
O H
O O
O N THYMINE
O P O N O
O
O H H
N
O N

O P O N O
O

CYTOSINE O
O
O P O

Ionophores are a class of compounds that form complexes with specific ions and facilitate their transport across cell membranes. An ionophore
typically has a hydrophilic pocket (or hole) that forms a binding site specific for a particular ion. 33
 IONPHORES
O
O O

O O
O

Valinomicine 18-crown-6

АМPHIPHILES

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