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History
The importance of supramolecular chemistry was established when
the three scientist i.e Jean-Marie lehn, J.Cram and J.Pedersen was
awarded with noble prize in 1987.
After that their work is recognised in this area.
In 1967, Pederson observed that crown ethers showed molecular
recognition.
Cram established Host-guest Chemistry where the host molecule can
accommodate another guest molecule.
In 1978, Lehn proposed the term ‘Supramolecular Chemistry’
“Supramolecular Chmeistry” is defined as “chemistry beyond the molecule”.
According to J.M. Lehn supramolecular chemistry is branch of the chemistry
which deals with the non covalent interactions.
In 1990, supramolecular chemistry become more sophisticated when the
researchers such as James Fraser develops molecular machinary and
molecular sensors.
Difference Between traditional chemistry and supra molecular
chemistry:
Supramolecular chemistry is the domain
of chemistry concerning chemical systems composed of
a discrete number of molecules. The strength of the forces
responsible for spatial organization of the system range from
weak intermolecular forces, electrostatic charge, or hydrogen
bonding to strong covalent bonding, provided that the electronic
coupling strength remains small relative to the energy
parameters of the component.
Whereas traditional chemistry concentrates on the covalent
bond, supramolecular chemistry examines the weaker and
reversible non-covalent interactions between molecules.
Supramolecular Chemistry
As we know that the traditional chemistry deals with the covalent bonding
while there is another branch of chemistry which deals with the non
covalent interactions known as supramolecular chemistry.
Molecular Recognition:
Molecular recognition refers to the specific interaction between two or
more molecules through non-covalent bonding such as hydrogenbonding
, metal coordination, hydrophobic forces, van der Waals forces, π- π
interactions, halogen bonding, electrostatic and electromagnetic effects. In
addition to these solvent also play a important role in molecular recognition.
The host and guest involved in molecular recognition exhibit molecular
complementarity.
Template-directed synthesis:
Molecular recognition and self-assembly may be used with reactive species in
order to pre-organize a system for a chemical reaction (to form one or more
covalent bonds).
It may be considered a special case of supramolecular catalysis. Non-covalent
bonds between the reactants and a "template" hold the reactive sites of the
reactants close together, facilitating the desired chemistry.
Synthesis Method:
1) Capping 3)Slipping
2)Clipping 4)Active Template
Capping:
Synthesis via the capping method relies strongly upon a thermodynamically
driven template effect i.e. "thread" is held within the "macrocycle" by non-
covalent interactions .
Clipping:
The clipping method is similar to the capping reaction except that in this case
the dumbbell shaped molecule is complete and is bound to a partial
macrocycle. The partial macrocycle then undergoes a ring closing
reaction around the dumbbell-shaped molecule, forming the rotaxane.
Slipping:
The method of slipping is one which exploits the thermodynamic stability of
the rotaxane. If the end groups of the dumbbell are an appropriate size it will
be able to reversibly thread through the macrocycle at higher temperatures.
By cooling the dynamic complex, it becomes kinetically trapped as a rotaxane
at the lower temperature.
"Active template" methodology:
Leigh and co-workers recently began to explore a strategy in
which template ions could also play an active role in promoting
the crucial final covalent bond forming reaction that captures the
interlocked structure.
Catenane:
A catenane is a mechanically-interlocked molecular architecture consisting of
two or more interlocked macrocycles, i.e. a molecule containing two or more
intertwined rings. The interlocked rings cannot be separated without breaking
the covalent bonds of the macrocycles. Catenane is derived from
the Latin catena meaning "chain".
Synthesis:
Application:
1) Molecular Device:
If we could create a molecular-size object that worked like an IC tip,
incredibly small computers with very high information densities could be
constructed.
Some of the most serious problems faced by
the world today, such as environmental pollution and energy
production, are atleast partially due to the large sizes of various
important devices, machines and apparatus.
One of the ultimate goals of those developing new devices is the
preparation of molecular devices, where molecules or molecular
systems replace functional units. Molecular devices are expected to
provide the key to the development of nanotechnology.
2)Molecular Machines – Supermolecules that can Catch Objects,
Move and Rotate