chemistry Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...

, mechanically-interlocked molecular architectures (MIMAs) are

molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...

s that are connected as a consequence of their

topology In mathematics, topology (from the Greek language, Greek words , and ) is concerned with the properties of a mathematical object, geometric object that are preserved under Continuous function, continuous Deformation theory, deformations, such ...

. This connection of molecules is analogous to keys on a

keychain A keychain (also key fob or keyring) is a small ring or chain of metal to which several keys can be attached. The length of a keychain allows an item to be used more easily than if connected directly to a keyring. Some keychains allow one or b ...

loop. The keys are not directly connected to the keychain loop but they cannot be separated without breaking the loop. On the molecular level, the interlocked molecules cannot be separated without the breaking of the

covalent bond A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...

s that comprise the conjoined molecules; this is referred to as a mechanical bond. Examples of mechanically interlocked molecular architectures include

catenane In macromolecular chemistry, 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 se ...

rotaxane In chemistry, a rotaxane () is a mechanically interlocked molecular architecture consisting of a dumbbell-shaped molecule which is threaded through a macrocycle (see graphical representation). The two components of a rotaxane are kinetically t ...

molecular knot In chemistry, a molecular knot is a mechanically interlocked molecular architecture that is analogous to a macroscopic knot. Naturally-forming molecular knots are found in organic molecules like DNA, RNA, and proteins. It is not certain that nat ...

s, and

molecular Borromean rings In chemistry, molecular Borromean rings are an example of a mechanically-interlocked molecular architecture in which three macrocycles are interlocked in such a way that breaking any macrocycle allows the others to dissociate. They are the smal ...

. Work in this area was recognized with the 2016

Nobel Prize in Chemistry ) , image = Nobel Prize.png , alt = A golden medallion with an embossed image of a bearded man facing left in profile. To the left of the man is the text "ALFR•" then "NOBEL", and on the right, the text (smaller) "NAT•" then "M ...

to Bernard L. Feringa,

Jean-Pierre Sauvage Jean-Pierre Sauvage (; born 21 October 1944) is a French coordination chemist working at Strasbourg University. He graduated from the National School of Chemistry of Strasbourg (now known as ECPM Strasbourg), in 1967. He has specialized in ...

, and

J. Fraser Stoddart Sir James Fraser Stoddart (born 24 May 1942) is a British-American chemist who is Board of Trustees Professor of Chemistry and head of the Stoddart Mechanostereochemistry Group in the Department of Chemistry at Northwestern University in ...

. The synthesis of such entangled architectures has been made efficient by combining

supramolecular chemistry Supramolecular chemistry refers to the branch 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 ...

with traditional covalent synthesis, however mechanically interlocked molecular architectures have properties that differ from both " supramolecular assemblies" and "covalently bonded molecules". The terminology "mechanical bond" has been coined to describe the connection between the components of mechanically interlocked molecular architectures. Although research into mechanically interlocked molecular architectures is primarily focused on artificial compounds, many examples have been found in biological systems including:

cystine knot A cystine knot is a protein structural motif containing three disulfide bridges (formed from pairs of cysteine residues). The sections of polypeptide that occur between two of them form a loop through which a third disulfide bond passes, forming ...

cyclotide In biochemistry, cyclotides are small, disulfide-rich peptides isolated from plants. Typically containing 28-37 amino acids, they are characterized by their head-to-tail cyclised peptide backbone and the interlocking arrangement of their three ...

s or lasso-peptides such as

microcin Microcins are very small bacteriocins, composed of relatively few amino acids. For this reason, they are distinct from their larger protein cousins. The classic example is microcin V, of ''Escherichia coli''. Subtilosin A is another bacterioci ...

J25 which are

proteins Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residues. Proteins perform a vast array of functions within organisms, including catalysing metabolic reactions, DNA replication, respo ...

, and a variety of

peptide Peptides (, ) are short chains of amino acids linked by peptide bonds. Long chains of amino acids are called proteins. Chains of fewer than twenty amino acids are called oligopeptides, and include dipeptides, tripeptides, and tetrapeptides. A ...

History

Experimentally the first examples of mechanically interlocked molecular architectures appeared in the 1960s with catenanes being synthesized by Wasserman and Schill and rotaxanes by Harrison and Harrison. The chemistry of MIMAs came of age when Sauvage pioneered their synthesis using templating methods. In the early 1990s the usefulness and even the existence of MIMAs were challenged. The latter concern was addressed by X ray crystallographer and structural chemist David Williams. Two postdoctoral researchers who took on the challenge of producing atenane (olympiadane) pushed the boundaries of the complexity of MIMAs that could be synthesized their success was confirmed in 1996 by a solid‐state structure analysis conducted by David Williams.

Mechanical bonding and chemical reactivity

The introduction of a mechanical bond alters the chemistry of the sub components of rotaxanes and catenanes.

Steric hindrance Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape ( conformation) and reactivity of ions ...

of reactive functionalities is increased and the strength of

non-covalent interactions In chemistry, a non-covalent interaction differs from a covalent bond in that it does not involve the sharing of electrons, but rather involves more dispersed variations of electromagnetic interactions between molecules or within a molecule. The c ...

between the components are altered.

Mechanical bonding effects on non-covalent interactions

The strength of non-covalent interactions in a mechanically interlocked molecular architecture increases as compared to the non-mechanically bonded analogues. This increased strength is demonstrated by the necessity of harsher conditions to remove a metal template ion from catenanes as opposed to their non-mechanically bonded analogues. This effect is referred to as the "catenand effect". This increase in strength of non-covalent interactions is attributed to the loss of

degrees of freedom Degrees of freedom (often abbreviated df or DOF) refers to the number of independent variables or parameters of a thermodynamic system. In various scientific fields, the word "freedom" is used to describe the limits to which physical movement or ...

upon the formation of a mechanical bond. The increase in strength of non-covalent interactions is more pronounced on smaller interlocked systems, where more degrees of freedom are lost, as compared to larger mechanically interlocked systems where the change in degrees of freedom is lower. Therefore, if the ring in a rotaxane is made smaller the strength of non-covalent interactions increases, the same effect is observed if the thread is made smaller as well.

Mechanical bonding effects on chemical reactivity

The mechanical bond can reduce the kinetic reactivity of the products, this is ascribed to the increased steric hindrance. Because of this effect

hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a Catalysis, catalyst such as nickel, palladium or platinum. The process is commonly employed to redox, reduce or S ...

of an alkene on the thread of a rotaxane is significantly slower as compared to the equivalent non interlocked thread. This effect has allowed for the isolation of otherwise reactive intermediates. The ability to alter reactivity without altering covalent structure has led to MIMAs being investigated for a number of technological applications.

Applications of mechanical bonding in controlling chemical reactivity

The ability for a mechanical bond to reduce reactivity and hence prevent unwanted reactions has been exploited in a number of areas. One of the earliest applications was in the protection of

organic dye A dye is a colored substance that chemically bonds to the substrate to which it is being applied. This distinguishes dyes from pigments which do not chemically bind to the material they color. Dye is generally applied in an aqueous solution and ...

s from

environmental degradation Environmental degradation is the deterioration of the environment (biophysical), environment through depletion of resources such as quality of air, water and soil; the destruction of ecosystems; habitat destruction; the extinction of wildlife; an ...

Examples

Olympiadane Olympiadane is a mechanically interlocked molecule composed of five interlocking macrocycles that resembles the Olympic rings. The molecule is a linear pentacatenane or a atenane. It was synthesized and named by Fraser Stoddart and coworkers ...

File:Rotaxane cartoon.jpg,

Rotaxane In chemistry, a rotaxane () is a mechanically interlocked molecular architecture consisting of a dumbbell-shaped molecule which is threaded through a macrocycle (see graphical representation). The two components of a rotaxane are kinetically t ...

File:CatenaneScheme.svg,

Catenane In macromolecular chemistry, 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 se ...

File:Trefoil knot arb.png,

Molecular knot In chemistry, a molecular knot is a mechanically interlocked molecular architecture that is analogous to a macroscopic knot. Naturally-forming molecular knots are found in organic molecules like DNA, RNA, and proteins. It is not certain that nat ...

File:Molecular Borromean Ring.png,

Molecular Borromean rings In chemistry, molecular Borromean rings are an example of a mechanically-interlocked molecular architecture in which three macrocycles are interlocked in such a way that breaking any macrocycle allows the others to dissociate. They are the smal ...