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Supramolecular Chemistry

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Supramolecular Chemistry Supramolecular Chemistry Rohit Kanagal Introduction Supramolecular Chemistry is one of the most rapidly growing areas of chemistry. This branch of chemistry emphasises on ‘chemistry beyond the molecule’ and ‘chemistry of molecular assemblies and the intermolecular bond’. Supramolecular Chemistry lends the idea of how molecules interact with one another. It aims to understand the structural and functional properties of systems that contain more than one molecular assembly. Phenomena such as molecular self-assembly, protein folding, molecular recognition, host-guest chemistry, mechanically-interlocked molecular architectures, and dynamic covalent chemistry are all integral parts of Supramolecular chemistry. These phenomena are controlled by certain non- covalent interactions between molecules such as ion-dipole, dipole-dipole interactions, van der Waals forces, hydrogen bonding, metal coordination, hydrophobic forces, pi-pi interactions, and various electrostatic effects. Over the last few decades, the ideas and studies of supramolecular chemistry have entered multiple fields such as chemical science, biological science, physical science, and material science. (Hasenknopf) An example of a supramolecular assembly Superamolecule A supramolecule or supramolecular assembly is a well-defined system of molecules that are held together with non-covalent intermolecular forces to form a bigger unit having its own organization, stability and tendency to associate or isolate. These are formed through the interactions between a molecule having convergent binding sites (such as hydrogen bond donor atoms and a large cavity) and another molecule having divergent binding sites (such as hydrogen bond acceptor atoms). The molecule having convergent binding sites is called host or receptor molecule while the molecule having divergent binding sites is called a guest or analyte molecule. The host can also be a macromolecule or a large aggregate of molecules while the guest is usually an ion (cation or anion) or a very small large aggregate of molecules. It’s the host molecule that binds a guest molecule through various non-covalent interactions to produce ‘Host-Guest’ complex or supramolecule. These host-guest interactions are seen in numerous biological processes such as enzyme-substrate, antibody-antigen interactions. (Bhalla, 2017) The well-defined complexes are generated by spontaneous self-assembly of the constituents under the given conditions. Self-assembly processes have recently gained great popularity in the field of nanotechnology. It is being utilized for the production of nano architectures of different shapes and sizes. Supramolecular chemistry and nanotechnology together form the field of nano-chemistry. Supramolecular Interactions A large number of non-covalent interactions strongly affect the structure and properties of supramolecular systems. These include hydrogen bonding, charge transfer complexes, van der Waals forces, and hydrophobic effect. These interactions have much lesser strength than covalent interactions. Thus, one weak interaction of this nature will have a negligible gain instability. However, when the small decrease in energy (stabilization) gained by one weak interaction is added to all small stabilizations from the other interactions, a stable architecture of a host-guest complex is formed. The formation of large complexes using supramolecular interactions is fast and much more stable as compared to the formation of complexes through other principles such as organic chemistry. Ion-Ion interactions Ion-ion interactions are interactions that occur between ions with opposite charges. It follows the basic principle that opposite charges attract and like charges repel. These forces operate over relatively long distances in the gas phase. This force is directly proportional to the product of the charges and inversely proportional to the square of the distance of separation between them. 푄 푄 퐹 ∝ 1 2 푅2 If two oppositely-charged particles are present in space (such as a sodium cation and a chloride anion), the attractive force between them will pull them together, and the force will increase as the two particles approach each other. Eventually, the 2 charges will stick together and a large amount of energy will have to be used to separate them again. They form an ion- pair which is also called an ionic compound. Ion dipole interactions Ion-dipole interactions are a result of the electrostatic interaction between a charged ion and a molecule that has a net dipole moment (asymmetrical charge distributions that arise in polar molecules causing it to develop partial positive and negative charges). Ionic compounds dissolved in polar liquids are the best example of this interaction in force. The partially negative end of a neutral polar molecule is attracted by the cation and the positive end of a polar molecule is attracted by the anion. Ion-dipole attractions are directly proportional to the charge on the ion and the magnitude of the dipole of the polar molecule. (Brilliant.org) Dipole-dipole interactions Ion-dipole interactions are a result of the electrostatic interaction between two molecules that have net dipole moments. Molecules arrange themselves in such a way that the positive end of one dipole aligns with the negative end of another, and vice versa. When the positive and negative dipoles approach each other, an attractive intermolecular interaction is created whereas when two positive dipoles or two negative dipoles approach each other a repulsive intermolecular interaction occurs. Dipole-dipole interactions and London dispersion forces together are called the Van der Waals forces. (Brilliant.org, Ion dipole interactions) London forces The London dispersion forces are the weakest intermolecular force. This force is a temporary force that occurs when the electron clouds of two near-by neutral atoms occupy positions that make the atoms form temporary dipoles. The force is also called as an induced dipole- induced dipole attraction. Although London forces are weak, they play a large role in many processes. They are the attractive forces that cause nonpolar substances to condense to liquids and to freeze into solids when the temperature is lowered. The Process The constant motion of electrons in an atom or molecule can cause the atom to develop an instantaneous dipole when its electrons are distributed unevenly around the nucleus. (PurdueUniveristy) A second near-by atom or molecule can be distorted by the dipole in the first atom or molecule due to electrostatic forces and induces a temporary dipole in the second atom. This leads to the electrostatic attraction between the two atoms or molecules. (PurdueUniveristy) Hydrogen bond Hydrogen bonds are a special and strong form of a dipole-dipole interaction that occurs when hydrogen is bonded to a highly electronegative atom. (Specifically N, O, and F. S and Cl can also form weak hydrogen bonds but they are very rare. Formation Of hydrogen bond (chem.libretexts.org) The hydrogen atoms in these compounds are bonded directly to a highly electronegative element, causing the hydrogen to acquire a large positive charge. O, N, and F atoms in these compounds are not only highly negatively charged, but they also have at least one lone pair. (chem.libretexts.org) Now if two of these compounds come together (2 water molecules for example) The hydrogen is highly attracted to the lone pair due to its δ+ charge. Although the attraction is significantly weaker than any type of intra-molecular bond, it is significantly stronger than an ordinary dipole-dipole interaction. Compounds with hydrogen bonds have relatively much higher boiling points as it takes more energy to overcome the force of attraction between two hydrogen-bonded molecules. This also explains some of the unique behaviors of many compounds. One example is that water exists in a liquid state due to hydrogen bonding. Hydrogen bonding also plays an important part in the properties and behavior of organic compounds such as alcohols, carboxylic acids, and amines. π–π Interactions Pi stacking (also called π–π Interactions) are non-covalent interactions that occur between aromatic rings through their pi bonds. These interactions are very important in nucleobase stacking in DNA and RNA molecules, and other biological processes such as protein folding, template-directed synthesis, materials science, and molecular recognition. (Wikipedia) Cation–π interaction Cation–π interaction is a noncovalent intermolecular interaction between an electron-rich π system (such as benzene) and a cation (such as Li+, Na+). The bonding energies of these interactions are very significant as the solution-phase values are very similar to the attraction from hydrogen bonds. Cation–π interactions also play an important role in nature. For example, they play a key role in molecular recognition and enzyme catalysis. (Wikipedia) Hydrophobic interactions Hydrophobic interactions are the interactions between water and hydrophobes. Hydrophobes are nonpolar molecules that have a long chain of carbons that do not interact with water molecules. A good example of this type of interaction would be the mixing of fat and water. (chem.libretexts.org) Origin/History The existence of intermolecular forces was first coined by Johannes Diderik van der Waals in 1873. However, it was Nobel laureate Hermann Emil Fischer who made the biggest advancements in the field of supramolecular chemistry. In 1890, Fischer suggested enzyme- substrate interactions take place in the
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