PHD
  1. Inorganic chemistry  1.1. Coordination chemistry  1.1.1. Ligand field theory  1.1.2. Crystal field theory  1.1.3. Molecular Orbital Theory for Coordination Compounds  1.1.4. Stability of Coordination Compounds  1.1.5. Electronic spectra of coordination compounds  1.1.6. Isomerism in Coordination Compounds  1.1.7. Kinetics and mechanism of coordination reactions  1.2. Organometallic Chemistry  1.2.1. Metal Carbonyls  1.2.2. Metal alkyl and aryl  1.2.3. Fischer and Schrock carbonaceans  1.2.4. Oxidative Addition and Reductive Elimination  1.2.5. Metal Hydrides  1.2.6. Catalysis by organometallic compounds  1.2.7. Metallocenes and Sandwich Complexes  1.2.8. CH activation  1.3. Solid state chemistry  1.3.1. Crystal structures and lattices  1.3.2. Band theory and electrical properties  1.3.3. Defects in the crystal  1.3.4. Synthesis of solid state materials  1.3.5. Magnetic and optical properties of solids  1.3.6. Superconductivity  1.3.7. Solid state ionics  1.4. Bio-inorganic chemistry  1.4.1. Metalloproteins and enzymes  1.4.2. Metal ion transport and storage  1.4.3. The role of metals in medicine  1.4.4. Bioinspired catalysis  1.4.5. Metal–DNA interactions  1.4.6. Metal Complexes in Medical Science  1.5. Lanthanides and Actinides  1.5.1. Electronic configuration and oxidation states in lanthanides and actinides  1.5.2. Spectral and Magnetic Properties in Lanthanides and Actinides  1.5.3. Separation and Extraction of Lanthanides and Actinides  1.5.4. Coordination chemistry of f-block elements  1.6. Main Group Chemistry  1.6.1. Chemistry of boron compounds  1.6.2. Chemistry of Silicon and Germanium Compounds  1.6.3. Chemistry of Phosphorus and Sulfur Compounds  1.6.4. Organosilicon chemistry  1.6.5. Noble Gas Chemistry
  2. Organic chemistry  2.1. Reaction mechanism  2.1.1. Nucleophilic substitution reactions  2.1.2. Electrophilic addition and substitution reactions  2.1.3. Elimination reactions  2.1.4. Rearrangement reactions  2.1.5. Radical reactions  2.1.6. Pericyclic Reactions  2.1.7. Photochemical reactions  2.2. Stereoscopic  2.2.1. Chirality and optical activity  2.2.2. Structural analysis  2.2.3. Stereoelectronic effects  2.2.4. Asymmetric synthesis  2.2.5. Dynamic Stereochemistry  2.3. Organometallic Chemistry in Organic Synthesis  2.3.1. Organolithium and organomagnesium reagents  2.3.2. Transition metal catalyzed coupling reactions  2.3.3. Palladium-catalyzed reactions  2.3.4. Olefin Metathesis  2.3.5. Gold and silver catalysis  2.4. Natural products chemistry  2.4.1. Alkaloids and terpenoids  2.4.2. Steroids and Flavonoids  2.4.3. Total synthesis of natural products  2.4.4. Biosynthesis of natural products  2.5. Supramolecular Chemistry  2.5.1. Host-Guest Chemistry  2.5.2. Self-assembly and molecular recognition  2.5.3. Supramolecular Catalysis  2.5.4. Molecular Machines
  3. Physical Chemistry  3.1. Thermodynamics  3.1.1. Laws of Thermodynamics  3.1.2. Chemical Potential and Equilibrium  3.1.3. Statistical thermodynamics  3.1.4. Non-equilibrium thermodynamics  3.2. Quantum Chemistry  3.2.1. Schrödinger equation and its applications  3.2.2. Molecular orbital theory  3.2.3. Density functional theory  3.2.4. Post-Hartree–Fock methods  3.3. Chemical kinetics  3.3.1. Reaction rate theory  3.3.2. Mechanism and rate laws  3.3.3. Catalysis and enzyme kinetics  3.3.4. Reaction dynamics  3.4. Spectroscopy and molecular structure  3.4.1. Infrared Spectroscopy  3.4.2. UV-visible spectroscopy  3.4.3. Nuclear Magnetic Resonance Spectroscopy  3.4.4. Mass Spectrometry  3.4.5. Raman Spectroscopy  3.5. Surface and Colloid Chemistry  3.5.1. Absorption and Catalysis  3.5.2. Surfactants and micelles  3.5.3. Colloidal Stability  3.5.4. Nanomaterials and Interfaces
  4. Analytical chemistry  4.1. Chromatography  4.1.1. Gas Chromatography  4.1.2. High Performance Liquid Chromatography  4.1.3. Thin Layer Chromatography  4.1.4. Ion Chromatography  4.2. Electroanalytical techniques  4.2.1. Voltammetry and Polarography  4.2.2. Conductometry and potentiometry  4.2.3. Colometry  4.3. Spectroscopic Methods  4.3.1. Atomic absorption spectroscopy  4.3.2. Fluorescence Spectroscopy  4.3.3. X-ray diffraction  4.3.4. Electron paramagnetic resonance spectroscopy  4.4. Chemometrics  4.4.1. Data processing and statistical methods  4.4.2. Multidisciplinary analysis  4.4.3. Machine Learning in Analytical Chemistry
  5. Theoretical and Computational Chemistry  5.1. Molecular dynamics simulation  5.2. Quantum chemistry methods  5.3. Computational drug design  5.4. Machine Learning in Chemistry  5.5. Ab initio molecular dynamics
  6. Biophysics and Medicinal Chemistry  6.1. Drug discovery and design  6.2. Enzyme kinetics and inhibition  6.3. Chemical biology approach  6.4. Protein-ligand interactions  6.5. Bioorthogonal chemistry
  7. Materials chemistry  7.1. Polymer chemistry  7.1.1. Polymerization mechanism  7.1.2. Functional Polymers  7.1.3. Biodegradable Polymer  7.1.4. Conducting and semiconducting polymers  7.2. Nano Chemistry  7.2.1. Nanoparticles and nanostructures  7.2.2. Carbon-based nanomaterials  7.2.3. Quantum dots  7.3. Energy and Environmental Chemistry  7.3.1. Battery and Fuel Cell Chemistry  7.3.2. Green chemistry and sustainable materials  7.3.3. Photocatalysis

PHD → Organic chemistry ↓


Supramolecular Chemistry


Supramolecular chemistry is a fascinating and wide-ranging branch of chemistry that focuses on the study of the structures and functions of molecules bound together through non-covalent interactions. Unlike traditional chemistry that emphasizes the formation of molecules through covalent bonds, supramolecular chemistry deals with interactions such as hydrogen bonding, van der Waals forces, π-π interactions, and electrostatic forces.

Introduction to supramolecular chemistry

The term "supramolecular chemistry" was popularized by Jean-Marie Lehn, who was awarded the Nobel Prize in Chemistry in 1987 for his developments in the field. At its core, supramolecular chemistry involves the investigation of molecular assemblies and complexes, describing how molecules combine together to perform functions that individual molecules cannot accomplish alone.

Non-covalent interactions

In supramolecular chemistry, non-covalent interactions play an important role. These include:

  • Hydrogen bond: A strong directional interaction in which a hydrogen atom is covalently bonded to an electronegative atom (such as oxygen or nitrogen).
  • Van der Waals forces: Weak forces arising from temporary dipoles in atoms and molecules.
  • π-π stacking: Interaction between aromatic rings where the electron clouds overlap.
  • Electrostatic force: Attraction between charged bodies, such as ions.
H - X···Y

Traditional hydrogen bond representation: A hydrogen donor (H) is attached to an electronegative atom (X) which interacts with the lone pair of another electronegative atom (Y).

Host-guest chemistry

One of the fundamental concepts of supramolecular chemistry is host-guest chemistry. It involves the interaction between a host molecule and a guest molecule, where the host often provides a cavity or pocket into which the guest fits.

Consider the example of cyclodextrin, which acts as a host molecule due to its hydrophobic pocket, allowing hydrophobic guest molecules to be contained:

[Host] + [Guest] ⇌ [Host·Guest Complex]

This equilibrium reflects the interaction between host and guest, leading to the formation of a complex structure, which is a fundamental idea in supramolecular chemistry.

Crown ethers and cryptands

Crown ethers and cryptands are classical examples of macrocyclic compounds that illustrate the principles of host-guest chemistry. Crown ethers are cyclic molecules that can tightly bind cations due to the electron-rich oxygen atoms within their structure.

example of a Crown Ether: C(OCH2CH2)n

These molecules are essential to understanding the principle of selectivity, since crown ethers can selectively bind specific cations depending on their size and charge.

Applications of supramolecular chemistry

The concepts of supramolecular chemistry have given rise to myriad applications in a variety of fields:

  • Drug delivery: Supramolecular systems can enhance the solubility, stability, and targeted delivery of drugs.
  • Molecular recognition: Key to sensor technology and catalysis by allowing specific interactions with target molecules.
  • Self-healing materials: Materials that can heal themselves through supramolecular interactions and rearrangements.

Example fragmentation

Consider a supramolecular system used in drug delivery:

Drug (D) + Cyclodextrin (CD) ⇌ CD-D Complex

In this system, cyclodextrin (CD) serves as a host to encapsulate the drug (D), increasing its solubility and stability.

Supramolecular polymers

Supramolecular chemistry has also led to the development of supramolecular polymers, which are polymer combinations created through non-covalent bonds. Unlike conventional polymers, these materials can be separated and reassembled, giving them incredibly unique properties.

  • Applications in making self-healing materials.
  • Use in reversible adhesives and smart materials.
  • Ability to respond to external stimuli (temperature, pH, light).

Visual example of a hydrogen bond network

 +---O--H···O---+n| OCCn|| \ COHnN

This figure shows a simplified diagram of hydrogen bonds forming a network. Each link represents a possible hydrogen bond, showing how molecules can come together through these interactions.

Challenges and future directions

Despite its successes, supramolecular chemistry remains challenging, especially in understanding and predicting the behavior of complex assemblies. Future research aims to:

  • Advancing computational models: Improved models for predicting supramolecular interactions.
  • Design of complex systems: Creating complex systems that mimic biological processes.
  • Sustainability: Using supramolecular chemistry for sustainable solutions such as efficient energy storage and conversion.

Conclusion

Supramolecular chemistry is a rich and evolving field with immense potential. Its principles encourage the exploration of molecular interactions beyond covalent bonding, providing innovative solutions to complex problems in science and technology. From drug delivery systems to self-healing materials, supramolecular chemistry continues to broaden our understanding of molecular science.


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Supramolecular Chemistry

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