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The molecular environment around a supramolecular system is also of prime importance to its operation and stability. Many solvents have strong hydrogen bonding, electrostatic, and charge-transfer capabilities, and are therefore able to become involved in complex equilibria with the system, even breaking complexes completely. For this reason, the choice of solvent can be critical. Molecular self-assembly is the construction of systems without guidance or management from an outside source other than to provide a suitable environment.

The molecules are directed to assemble through non-covalent interactions. Self-assembly may be subdivided into intermolecular self-assembly to form a supramolecular assembly , and intramolecular self-assembly or folding as demonstrated by foldamers and polypeptides.

Molecular self-assembly also allows the construction of larger structures such as micelles , membranes , vesicles , liquid crystals , and is important to crystal engineering. Molecular recognition is the specific binding of a guest molecule to a complementary host molecule to form a host—guest complex. Often, the definition of which species is the "host" and which is the "guest" is arbitrary.

The molecules are able to identify each other using non-covalent interactions. Key applications of this field are the construction of molecular sensors and catalysis. 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.

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This technique is particularly useful for situations where the desired reaction conformation is thermodynamically or kinetically unlikely, such as in the preparation of large macrocycles. This pre-organization also serves purposes such as minimizing side reactions, lowering the activation energy of the reaction, and producing desired stereochemistry.

After the reaction has taken place, the template may remain in place, be forcibly removed, or may be "automatically" decomplexed on account of the different recognition properties of the reaction product. The template may be as simple as a single metal ion or may be extremely complex. Mechanically interlocked molecular architectures consist of molecules that are linked only as a consequence of their topology.

Some non-covalent interactions may exist between the different components often those that were utilized in the construction of the system , but covalent bonds do not. Supramolecular chemistry, and template-directed synthesis in particular, is key to the efficient synthesis of the compounds. Examples of mechanically interlocked molecular architectures include catenanes , rotaxanes , molecular knots , molecular Borromean rings [20] and ravels. In dynamic covalent chemistry covalent bonds are broken and formed in a reversible reaction under thermodynamic control.

While covalent bonds are key to the process, the system is directed by non-covalent forces to form the lowest energy structures. Many synthetic supramolecular systems are designed to copy functions of biological systems. These biomimetic architectures can be used to learn about both the biological model and the synthetic implementation.

Examples include photoelectrochemical systems, catalytic systems, protein design and self-replication. Molecular imprinting describes a process by which a host is constructed from small molecules using a suitable molecular species as a template. After construction, the template is removed leaving only the host. The template for host construction may be subtly different from the guest that the finished host binds to. In its simplest form, imprinting utilizes only steric interactions, but more complex systems also incorporate hydrogen bonding and other interactions to improve binding strength and specificity.

Molecular machines are molecules or molecular assemblies that can perform functions such as linear or rotational movement, switching, and entrapment. These devices exist at the boundary between supramolecular chemistry and nanotechnology , and prototypes have been demonstrated using supramolecular concepts. Fraser Stoddart and Bernard L. Feringa shared the Nobel Prize in Chemistry for the 'design and synthesis of molecular machines'.

Supramolecular systems are rarely designed from first principles. Rather, chemists have a range of well-studied structural and functional building blocks that they are able to use to build up larger functional architectures. Many of these exist as whole families of similar units, from which the analog with the exact desired properties can be chosen.

Macrocycles are very useful in supramolecular chemistry, as they provide whole cavities that can completely surround guest molecules and may be chemically modified to fine-tune their properties. Many supramolecular systems require their components to have suitable spacing and conformations relative to each other, and therefore easily employed structural units are required. Supramolecular chemistry has found many applications, [31] in particular molecular self-assembly processes have been applied to the development of new materials.

Large structures can be readily accessed using bottom-up synthesis as they are composed of small molecules requiring fewer steps to synthesize. Thus most of the bottom-up approaches to nanotechnology are based on supramolecular chemistry.


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Review of the hardback: 'Supramolecular Organization and Materials Design edited by William Jones and Chintamani Rao demonstrates the importance of supramolecular chemistry and self-organization in the design and synthesis of novel organic, inorganic, and biomaterials. The bottom-up approach of supramolecular context of the synthesis of new materials and function-specific molecular devices With more than references, this book should be compulsory reading for any senior university undergraduate on a materials chemistry course and will be an inspiration for any graduate student beginning research in this area.

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Function materials and systems - new options through supramolecular chemistry

Supramolecular Chemistry deals with the design, synthesis and study of molecular structures held together by non-covalent interactions. With contributions from leading workers in the field, the book shows how the bottom-up approach of supramolecular chemistry can be used to synthesize not only new materials, but function specific molecular devices as well.

This book will be of interest to researchers and graduate students in chemistry, materials science and physics who need a summary of the most recent developments in the field. Seller Inventory AAV More information about this seller Contact this seller. Book Description Cambridge University Press, Condition: Brand New.

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