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Host–guest chemistry

physical science Maturity 9-11 Next article →

Host–guest chemistry is a specialized branch of supramolecular chemistry. It focuses on complexes made of two or more molecules or ions. These components are held together by unique structural relationships. Unlike many chemical reactions, these components are not joined by full covalent bonds. Instead, they rely on non-covalent bonding to stay together. This concept includes molecular recognition, where a host specifically selects a particular guest. This process is vital for life because it maintains the 3D structure of large molecules like proteins.

Encapsulating Assembly ChemEurJ 1996 v2 p989
Encapsulating Assembly ChemEurJ 1996 v2 p989

The mechanism of host–guest interaction relies on several types of non-covalent forces. These forces include ionic bonding, hydrogen bonding, van der Waals forces, and hydrophobic interactions. In many cases, the host is a larger molecule with a pore-like structure. This cavity captures a smaller guest molecule. The interaction often exists in a dynamic equilibrium. This means the host and guest constantly move between being bound and unbound. This state is represented by the equation H + G ⇌ HG, where H is the host and G is the guest.

Scientists categorize many different types of host molecules. Macrocyclic hosts are a major group of these molecules. Cyclodextrins are tubular hosts made of glucose units connected by ether bonds. There are three main types: alpha-CD, beta-CD, and gamma-CD. These differ by their cavity sizes, which are 5, 6, and 8 Å, respectively. Cucurbiturils are another type of macrocycle. They are made of glycoluril monomers linked by methylene bridges. Their oxygen atoms tilt inward to create a cavity.

Cucurbit-6-uril ActaCrystallB-Stru 1984 382
Cucurbit-6-uril ActaCrystallB-Stru 1984 382

Other hosts create more rigid or cage-like environments. Inclusion compounds occur when a host has a cavity for a guest, often using van der Waals bonding. Clathrates are related compounds that use a lattice to trap molecules. The name comes from the Latin word for "with bars, latticed."

Cd(CN)2CCl4
Cd(CN)2CCl4

Some clathrates, like Hofmann clathrates, use small aromatic guests like benzene. Others, like silica clathrasil, are found in marine sediments. Zeolites are also important hosts. They are rigid aluminosilicates with open framework structures used for catalysis. Even small molecules like urea can form hydrogen-bonded tunnels to host organic guests.

Molecular encapsulation occurs when a guest is confined within a host. This process can change how a guest molecule behaves. In a solution, some molecules react too quickly to be studied. However, encapsulation can stabilize these molecules. For example, cyclobutadiene is normally highly unstable in solution. It can be isolated at room temperature if it is encapsulated.

Nitrobenzene bound within hemicarcerand from Chemical Communications (1997)
Nitrobenzene bound within hemicarcerand from Chemical Communications (1997)

Large assemblies called metallaprisms are also being studied. These have flexible cavities and show promise for delivering drugs to cancer cells. Some molecular capsules are even built like an egg shell. They use salt bridge interactions to self-assemble and remain stable up to 60 °C.

Chem540, Egg Schell2
Chem540, Egg Schell2

Crown ethers represent another distinct class of hosts. These molecules are specifically known for binding cations, which are positively charged ions. Small crown ethers like 12-crown-4 bind to small ions such as Li+. Larger versions like 24-crown-8 bind better to larger ions. They can also bind to neutral molecules like 1, 2, 3-triazole. When a crown ether is threaded by a linear molecule, it forms a structure called a rotaxane. In these structures, the crown ether is not permanently bound. It can actually move up and down the threading molecule.

Researchers use specific tools to study these interactions. Nuclear magnetic resonance (NMR) spectroscopy is used to observe chemical shifts. This helps determine the concentration of the host-guest complex. Ultraviolet-visible (UV-vis) spectroscopy is also common. It uses the Beer–Lambert law to calculate concentrations based on light absorbance. Scientists use these methods to calculate the equilibrium constant, K. This constant tells us how stable the host-guest complex is. By measuring these values, chemists can design better materials for medicine and industry.

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🖼️ Images & Media (12)
File:Cucurbit-6-uril ActaCrystallB-Stru 1984 382.jpg
Cucurbit-6-uril ActaCrystallB-Stru 1984 382.jpg
File:Encapsulating Assembly ChemEurJ 1996 v2 p989.jpg
Encapsulating Assembly ChemEurJ 1996 v2 p989.jpg
File:Cd(CN)2CCl4.jpg
Cd(CN)2CCl4.jpg
File:Nitrobenzene bound within hemicarcerand from Chemical Communications (1997).jpg
Nitrobenzene bound within hemicarcerand...
File:Fig_1_threading_of_macrocyclic_ring.png
Fig_1_threading_of_macrocyclic_ring.png
File:Chem540f09capcartoon.png
Chem540f09capcartoon.png
File:Chem540,_Egg_Schell2.png
Chem540,_Egg_Schell2.png
File:Nmr titration.gif
Nmr titration.gif
File:UV-vis spectrum of host-guest binding.jpg
UV-vis spectrum of host-guest binding.jpg
File:Fig_3_self-healing_mechanism.png
Fig_3_self-healing_mechanism.png
File:Sensing.png
Sensing.png
File:IDA Dyes.png
IDA Dyes.png
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