Supramolecular-Architecture and Self

Assembly

towards NANOTECHNOLOGY

Prof. L Cronin – Lecture 1

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 Nanotechnology is:

• The science and engineering of creating materials,

functional structures and devices on the nanometer
scale. Examples include carbon nanotubes,
nanocrystals, quantum dots, molecular clusters.

• The “top down” manufacturing paradigm; Molecular

engineering, molecular electronics, nano- fabrication,
bionanotechnology. Imaging and manipulating at the
atomic scale.
 Nanotechnology
• The essence of nanotechnology is the ability to work
at the molecular level, atom by atom, to create large
structures with fundamentally new molecular
organization.

• Compared to the behavior of isolated molecules of

about 1 nm or of bulk materials, behavior of structural
features in the range of about 10-9 to 10-7 m (1 to 100
nm) exhibit important differences that are not yet fully
explained by explained by theory.
 Topics to be covered
• Fundamental interactions utilized in molecular assemblies; coordinate
bonds, hydrogen bonding, electrostatic interactions, hydrophobic
interactions etc.

• Cooperative interactions in the formation of supra-molecules; concepts of

kinetic and thermodynamic control in assembly and template effects.

• The building block concept in the formation of supramolecular molecules;

the interplay of molecular shape, symmetry and topology, discussion of
virtual combinatorial libraries.

• Biological self assembly in the context of protein folding, virus assembly and
some examination of the assembly of DNA and other networks

• Understand the requirements to design building blocks that can form

supramolecular architectures

• The application of supramolecular molecules as molecular devices,

molecular machines and functional materials and as drugs
Nano-scale
 What is Supramolecular Chemistry ?

“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”
J.-M- Lehn

"Supramolecular chemistry is defined as chemistry

‘beyond the Molecule’, as chemistry of tailor
shaped inter-molecular interaction.”

F. Vögtle
 What is supramolecular chemistry?
Where did it come from?
Why does it deserve to be a field of study all its own?

• the study on non-covalent & intermolecular forces and the

structures created by these forces: “chemistry beyond the
molecule”

• inspired from biology and built on the shoulders of

traditional synthetic organic chemistry

• the next logical step in synthetic chemistry; understanding

and interface with the biological world; nanotechnology
 Metallosupramolecular chemistry
The ultimate goal of metallosupramolecular chemistry, as in the
supramolecular chemistry of organic systems, is to assemble metal
complexes that may be applied to various tasks at hand, e.g., light
harvesting, cation and anion sensing, and the photosplitting of water. The
key to any supramolecular system is that the properties of the individual
sub-units are still found in the final structure, i.e., that we still have a
supramolecular system and not a ‘supermolecule’
 Supermolecules
A ‘supermolecule’ may still possess interesting
properties or functions, but is not composed of
independent subunits that work in together to deliver
supramolecular properties.
 Information Storage

The ultimate supramolecular material?

• Encodes gigabytes of data

• Can Self-Replicate

• Built-in Error Correction

• Is the basis of life

Watson & Crick 1953

 Catalysis

Enzymes: Biological Catalysts with remarkable

efficiency and selectivity.
“Smart” Nanostructured Materials

Tobacco Mosaic Virus (TMV)

 The potential payoff:

• Molecular Data Storage & Data Transmission

• Nano-Machines

• High efficiency, high selectivity, “green” catalysts

• Molecular Sensors

• Separation Devices

• Drug & Gene delivery

• Next generation medicine (replacement organs, etc.)

 Emil Fischer: The Lock & Key
1894: Recognized even before molecular structure was
well understood that shape matters.

In order for two species to interact in a specific fashion,

they must have complementary shape & chemistry like a
key fitting into a lock.

Wins Nobel Prize in 1902.

 1987 Nobel Prize

1987 Nobel prize in chemistry goes to:

* Donald J. Cram (1919-2001), UCLA, USA

* Jean-Marie Lehn (1939-), U. Louis Pasteur,

France

* Charles J. Pedersen (1904-1989), Du Pont, USA

“for their development and use of molecules with

structure-specific interactions of high selectivity”

http://www.nobel.se/chemistry/laureates/1987/index.html
Charles J. Pedersen: Crown Ethers

O O

O O

Dibenzo-18-Crown-6
Charles J. Pedersen: Crown Ethers
O

O O

O O Oxygen atoms donate

a fraction of their
O electron density to
O O
electron deficient
O O
species such as alkali
O cations: Li, Na, K
O

O O
Q: Why did he get selectivity
for different ions?
O O

O O
 Charles J. Pedersen

• Discovered essentially by accident

• Think about structure. 3D shape. Geometry.
• Computer simulations and CPK models
• Prepared an entire series of crown-ethers each with
their own particular selectivity for various cations
• Selectivity base primarily on size:

Li 1.36Å 14-crown-4 1.2-1.5Å

Na 1.94Å 15-crown-5 1.7-2.2Å
K 2.66Å 18-crown-6 2.6-3.2Å

It’s easy: some fit some don’t

Donald J. Cram: Pre-organization

OR
OR RO

OR RO
OR

“Spherand” - preorganized binding site

Selectivity for Li+ > Na+ >> K+
Q: What did he mean by preorganized?
 Donald J. Cram

• Synthesized a huge series of increasingly complicated

host-guest systems that bind molecules instead of just ions
and eventually tries to emulate an enzyme catalytic site.

• Introduces the idea of a “carcerand” - synthetic molecular

(jail) cells. Q: What other carcerands can you think of?

• Primary contribution is to show how important

preorganization is to binding strength.

• Shows the application of some hosts for practical

application: resolution of racemic mixtures
How do you tell which is a host & which is a guest?

Host binding sites face inward, or converge

Guest binding sites face outward, or diverge

Complex Two or more molecules held together

in a unique structural relationship by
non-covalent (weak) forces.
 Self Assembly
• Molecular Self Assembly

– the spontaneous assembly of supramolecular molecules

and networks

– Dependent or thermodynamic and kinetic considerations

– Building blocks X
X X

– Templates X X
X
 Forces involved in self assembly
• Hydrogen bonding
– Strong N-H…F, moderate N-H…OH and weak C-H…Cl-

• Pi-stacking interactions

• Electrostatic (ion-ion, ion-dipole and dipole-diple)

• Dispersion and induction forces (van der Waals)

• Coordinate bonding

• Hydrophobic or solvatophobic effects

 Interaction Energies
• Bond energy of a single covalent bond X-Y
– 350 kJ mol-1
• Bond energy of a triple bond e.g N2 942 kJ mol-1

• Non-covalent interactions can range from 2 kJ mol-1

to 20 kJ mol-1 for a hydrogen bond and 250 kJ mol-1
for an ion-ion interaction

• POWER OF SUPRAMOLECULAR CHEMISTRY is in

the combination of a number of these interactions
 Example of electrostatic interactions
- Valinomycin
Valinomycin (VM) is a dodecadepsipeptide,
that is it is made of twelve alternating amino
acids and hydroxy acids to form a
macrocyclic molecule. It is a member of the
group of natural neutral ionophores because
it doesn't have a residual charge.

It is a naturally occurring macrocylic antibiotic

that selectively transports potassium cations
across mitochondiral membranes in the
PRESENCE of sodium cations

Confromation of Valinomycin is stabilised by

NCO…HN hydrogen bonds. K+ is bound by
the O= atoms of the ester groups
 Valinomycin
• K+ is complexed by the ester group oxygen atoms

• Once complexed it can be efficiently transported

throughthe hydrophobic membrane.

• The membrane is lipophilic and so will not normally

allow charged species to pass through

• The exterior has greasy alkyl groups providing the

complex with solubility
 Metallosupramolecular chemistry
The term « metallosupramolecular chemistry » was
coined in the early 90s to describe supramolecular
coordination chemistry. This sub-field of
supramolecular chemistry started off by examining the
metal-directed self-assembly of discrete structures and
soon expanded to infinite structures. Although metal
directed self-assembly proved to be a powerful tool to
build up large supramolecular structures, the true goal
has always been the assembly of architectures with
specific functions.