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Unit – 3 – SPECTROSCOPY AND

MOLECULAR SWITCHES
LEARNING CONCEPT – 1
Introduction to spectroscopy - Electromagnetic radiation – wave and particle nature – Dispersion of light -
Electromagnetic spectrum –
Key Words: Electromagnetic radiations, Wave and Particle properties, dispersion of light, electromagnetic spectrum

Introduction
Spectroscopy is the study of the interaction between matter and electromagnetic radiation. By this, we can determine the
composition, structure, and properties of matter.
In other words, spectroscopy is a combination of two words namely; scopy and spectra, which means the study of
the spectrum.
Spectrum is the arrangement of energy radiations in their increasing order or decreasing order.

Electromagnetic Radiations
These are the forms of energy that can travel with high velocities. They are useful in the determination of many phenomena.
They usually have dual nature, i.e., both wave nature and particle nature. It consists of electrical and magnetic waves
perpendicular to each other.
An electromagnetic wave is characterized by the following
parameters.
(i). Wavelength: It is the distance between two successive
maxima on an electromagnetic wave. It is denoted by ‘λ’. The
units of wavelength are m, cm, mm, μm, nm and Å.
The beam carrying radiation of only one discrete wavelength
is said to be monochromatic, otherwise called polychromatic.
(ii). Frequency: The number of wavelength units passing
through a given point in unit time is called the frequency of
radiation. It is denoted by ‘ʋ’.
It is generally expressed in cycles per second or Hz.
(iii). Wavenumber: It is defined as the number of waves per
centimeter in vacuum. It is denoted by ‘ῡ’.
1
ῡ= 𝜆
(iv). Velocity: the product of wavelength and frequency is equal to the velocity of the wave in the medium.
∴𝑣= 𝜈× 𝜆
Units of velocity is cm.s-1 or m.s-1

PARTICLE PROPERTIES OF ELECTROMAGNETIC RADIATION

Electromagnetic radiation consists of a stream of discrete packets of pure energy, called photons or quanta.
The energy of photon is proportional to the frequency of radiation and is given by

𝐸 = ℎ. 𝜈
E is the energy of photon, ν is the frequency of electromagnetic radiation and h is the Planck’s constant.

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RELATIONSHIP BETWEEN WAVELENGTH AND PARTICLE PROPERTIES OF ELECTROMAGNETIC RADIATION

The relationship between wavelength and particle properties of electromagnetic radiation is given by
ℎ. 𝑐
𝐸 = ℎ. 𝜈 = ℎ. 𝑐. ῡ =
𝜆
ELECTROMAGNETIC SPECTRUM
Electromagnetic waves can be classified and arranged according to their various wavelengths or frequencies; this
classification is known as the electromagnetic spectrum. The following table shows us this spectrum, which consists of all
the types of electromagnetic radiation that exist in our universe.

Light that we can see with our eyes—makes up only a small fraction of the different types of radiation that exist. Radio
waves have the longest wavelength, and gamma rays have the shortest wavelength.

DISPERSION OF LIGHT

The dispersion of light is the phenomenon of splitting of a beam of white light into its seven constituent colors when passed
through a transparent medium. A beam of sunlight through a glass prism. The glass prism split the light into a band of seven
colors, known as spectrum.

Thus, the spectrum is a band of seven colors which is obtained by splitting of white light by a glass prism. The order of
colors from the lower end of spectrum is violet (V), indigo (I), blue (B), green (G), yellow (Y), orange (O), and red (R). The
sequence of the 7 colors so obtained in a spectrum can be remembered by using the acronym ‘VIBGYOR’.

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Unit – 3 – SPECTROSCOPY AND

MOLECULAR SWITCHES
LEARNING CONCEPT – 2 Types of Energies in a molecule
Classification – Absorption and Emission spectroscopy. Molecules have energy in different forms which are described
Key Words: Absorption Spectrum, Emission Spectrum, as

a). Translational energy (Etrans): It is concerned with the overall movement of the molecules along the three axes. It is
significant only in gases and to lesser extent in liquids.

b). Rotational energy (Erot): It involves the spinning of the molecules about the axes passing through their center of gravity.

c). Vibrational energy (Evib): It is associated with the vibrations within a molecule such as stretching or the bending of the
bonds.

d). Electronic energy (Eelec): It involves the changes in the distribution of electrons by promotion of electrons to higher-
energy levels on absorption of energy.

If E is the energy of the molecule, then E = Etrans + Erot + Evib + Eelec and Etrans > Erot > Evib > Eelec

INTERACTION OF ELECTROMAGNETIC RADIATION WITH MATTER

When electromagnetic radiation passes through matter, a variety of phenomenon may occur.

(i). If the photons of radiation possess the appropriate energies, they may be absorbed by the matter and result in
electronic transitions, vibrational or rotational changes or combination of all. After absorption, atoms or molecules excite
and quickly give out energy in the form of heat or electromagnetic radiation.

(ii). The energy may be not be absorbed completely, but may be scattered or reflected.

(iii). Electromagnetic radiation may bring a change in orientation or polarization.

(iv). In some cases, they may bring the phenomenon of fluorescence or phosphorescence.

S. No Changes brought about Changes observed in Technique

UV – Visible region – UV – Visible
1 Electronic energy level changes Absorption
Spectroscopy
2 Vibrational energy changes IR – region – IR Spectroscopy Absorption
Radio Frequency region – NMR
3 Rotational energy level changes Absorption
Spectroscopy
4 Scattering or Reflection Visible region Emission
5 Polarization Visible region Emission
Fluorescence or
6 Visible region Emission
Phosphorescence

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The electromagnetic spectrum consists of radiations of different wavelengths and frequencies can be separated by using
an instrument called spectroscope or spectrograph. A spectroscope consists of a prism or diffraction grating for dispersion
od radiations and telescope to examine emergent radiations with human eye or for photograph. Spectrum is nothing but
pattern giving components of radiation.

Classification of Spectra
Spectra can be broadly classified as
a). Absorption Spectrum
b). Emission Spectrum

Absorption Spectrum
• When a substance is irradiated with electromagnetic radiation, the energy of the incident photon may be
transferred to the molecule, raising them from ground state to an excited state.
• This process is known as absorption and the resultant spectrum is known as absorption spectrum.
• Energy absorption occurs only when the energy difference between the ground state and higher energy level is
exactly equal to the energy of the incident electromagnetic radiation.
• Absorption spectrum is used for the structural elucidation of molecules.

Emission Spectrum
• Molecules give emission spectra when subjected to intense heat or
electric discharge.
• The molecule obtains the necessary energy to become excited and
move from lower energy state to higher energy state.
• On returning to the lower energy state, molecules may emit
radiations and is the result of transition of molecule from excited
state to one of its lower energy states.
• The excess energy is emitted as a photon and the corresponding
frequency is recorded as emission spectrum.
•
If the transition is from upper energy level (E2) to lower energy level (E1), the frequency (ʋ) of the emission spectrum is
given by
𝐸2 − 𝐸1 𝛥𝐸
ʋ= =
ℎ ℎ

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Differences between emission and absorption spectra

Feature Emission Spectrum Absorption Spectrum

Energy
Loses energy Gains energy
Change
Appearance Bright lines on dark background Dark lines on bright background
Information Energy levels of the atom/molecule Energy levels the atom/molecule can absorb
Identifying elements in stars and other celestial Identifying substances in solutions.
objects. Measuring the concentration of substances in
Analyzing the composition of materials. solutions.
Applications Creating lasers. Studying the structure of molecules.

Plots

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Unit – 3 – SPECTROSCOPY AND

MOLECULAR SWITCHES
LEARNING CONCEPT – 3 THEORIES OF ABSORPTION
Laws of Absorption – Derivation of Beer – Lambert’s When light is incident upon a homogeneous medium, a part of
law – Significance. the light is reflected, a part light is absorbed by the medium and
Key Words: Beer – Lambert’s law – Significance- the remaining is allowed to transmit as such.
Deviations If 𝐼0 denotes the incident light, 𝐼𝑟is the reflected light, 𝐼𝑎 is the
absorbed light and 𝐼𝑡 is the transmitted light. Then
𝐼0 = 𝐼𝑟 + 𝐼𝑎 + 𝐼𝑡
If a comparison cell is used, then intensity of reflected light becomes very small and can be eliminated. Hence,
𝐼0 = 𝐼𝑎 + 𝐼𝑡
LAMBERT’S LAW
“When a beam of light is allowed to pass through a transparent medium, the rate of decrease of intensity with the thickness
of medium is directly proportional to the intensity of the incident light”.
Mathematically,
𝑑𝐼
− ∝𝐼
𝑑𝑡
𝑑𝐼
⇒− =𝑘∙𝐼
𝑑𝑡
Where I denote the intensity of incident wavelength λ, t denotes the thickness of the medium and k denotes the
proportionality constant.
On integrating the above equation, we get,
− ln 𝐼 = 𝑘𝑡 + 𝐶
C is the integration constant.
At t = 0, I = I0 and C = -ln I0
Substituting the of C in the above equation, we get
− ln 𝐼 = 𝑘 𝑡 − ln 𝐼0
𝐼
ln = −𝑘. 𝑡
𝐼0
𝐼 1
log = − 𝑘𝑡
𝐼0 2.303
Where 𝐼0 denotes the intensity of the incident light, 𝐼 denotes the intensity of the transmitted light and k is a constant which
depends upon the wavelength and absorbing medium used.
𝑘 𝐼
Also, k’ = 2.303 , is called as extinction coefficient and − log 𝐼 is termed as absorbance of the medium and is represented
0
by A.
∴ 𝐴 = 𝑘′. 𝑡
The above equation is termed as Lambert’s law.

BEER’S LAW
“When a beam of monochromatic light is made to pass through a homogeneous medium, the decrease in intensity of
incident light with respect to thickness of the medium is directly proportional to the concentration of the solution”.

Mathematically,
𝑑𝐼
− ∝𝑐
𝑑𝑡

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c is the concentration of the solution. Integrating the above solution, at boundary conditions, we get

∴ 𝐴 = 𝑘′. 𝑐

The above equation is also known as Beer’s law.

Combining the two equations of Lambert’s law and Beer’s law, we get
∴ 𝐴 = 𝑘. 𝑘 ′ . 𝑐. 𝑡

∴ 𝐴 = 𝜀. 𝑐. 𝑡

Where ε is known as molar extinction co-efficient. The above equation is Beer – Lambert’s law.

LIMITATIONS
1. The law has no idea bout the effect of temperature, nature of the solvent and wave – length of the energy
radiation.
2. The molar extinction co-efficient value (ε) is constant and does not depend on the concentration of the analyte,
pathlength and intensity of incident radiation.

Beer – Lambert’s Plot

A graph is drawn by taking concentration of analyte on X – axis and corresponding absorbance values on Y – axis. The
graph will be a straight line passing through origin.

Deviations of Beer – Lambert’s law:

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The deviations in beer – lambert’s law may be because of

a. Interaction of solute and solvent
b. Interaction between solute molecules and
c. May be due to inter molecular forces.

Curve (a) – Chemical Deviation (Positive deviation)

The is may be due to hydrolysis, association, polymerization, ionization or due to hydrogen bonding.

Curve (b) – Ideal conditions

This is valid for dilute solutions in real time applications. At higher concentrations, the substance absorbs more readily than
that expected on the basis of Beer‘s law.

Curve (c) – Instrumental Deviation (Negative deviation)

This is observed when polychromatic radiation is used. When Illumination is not monochromatic, negative deviations will
occur

Problems

1. Calculate the frequency, wavenumber and energy corresponding to a wave of wavelength 8000Å.
2. Calculate the molar absorptivity of the solution of KMnO4, showing an absorbance of 0.485, whose
concentration is 0.0025M. the path length of the cell is 1cm.
3. Vividh Bharathi Broadcasting Corporation operates its programs at a frequency of 600MHz. Express the same in
units of wavelength and wave number.
4. Molar absorptivity of a solution of K2Cr2O7 was observed to be 1 × 106 lit / mol/cm at 445 nm. When placed in
a cell of path length of 1 cm. Calculate the concentration of K2Cr2O7 when its absorbance is 0.545.

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Unit – 3 – SPECTROSCOPY AND

MOLECULAR SWITCHES
LEARNING CONCEPT – 4-5
UV – Visible Spectroscopy - 1 – Introduction to UV – Visible Spectroscopy – Principle involved in UV – Visible
Spectroscopy.

Introduction
Basically, spectroscopy is related to the interaction of light with
matter. As light is absorbed by matter, the result is an increase in the energy
content of the atoms or molecules.
Ultraviolet-visible spectroscopy is considered an important tool in
analytical chemistry. this is one of the most commonly used techniques in
clinical as well as chemical laboratories. This tool is used for the qualitative
analysis and identification of chemicals.
Its main use is for the quantitative determination of different organic
and inorganic compounds in solution. This technique is regarded as an
absorptive spectrophotometric technique. The absorption of visible light or
ultraviolet light by a chemical compound will produce a distinct spectrum.

Principle of UV-Visible Spectroscopy

UV-Visible spectroscopy is based on the principle of absorption of ultraviolet (UV) and visible light by molecules, atoms, or
ions in a sample.
When electromagnetic radiation in the UV (200-400 nm) or visible (400-800 nm) range passes through a sample, certain
wavelengths are absorbed. This absorption occurs due to the excitation of electrons from a lower energy state (ground
state) to a higher energy state (excited state).

𝐡ʋ = 𝚫𝐄 = 𝐄𝟐 − 𝐄𝟏
Electronic transitions in a molecule

Theoretically possible electronic transitions are

1. σ→ σ*:
2. π → π*
3. π→ σ*
4. σ →π*
5. n→ σ*
6. n→ π*

Experimentally possible electronic transitions

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Where σ and σ* represents bonding and anti-bonding orbital’s of σ bonding electrons, π and π* are bonding and anti-
bonding orbital’s of π bonding electrons, n denotes nonbonding electrons.Experimentally, possible electronic transitions in
organic molecules are as shown in the above figure

UV – Visible Spectrum:
UV- Visible spectrum is a plot of intensity vs wavelength.
In UV- Visible spectrum signals appear with broadness
instead of sharp vertical lines.
The middle point of UV-Visible band at which absorption of
radiation is maximum is called λ max.

Instrumentation of UV – Visible Spectroscopy

1. Source
Following are the requirements of a radiation source.
• It must be stable.
• It should have sufficient intensity for transmitted radiation to be detected
• It must be continuous in entire wavelength
• Commonly used sources are tungsten lamp (for visible region) and Hydrogen or deuterium lamp (for UV region).

2. Monochromator
The function of the monochromator is to break the polychromatic radiation into component wavelengths or bands of
wavelengths.
The essential components of a monochromator are Entrance slit, Collimating device, a prism or grating, a focusing lens
and an exit slit.

3. Sample Holder
Samples to be studied in UV – Visible spectroscopy are usually put in cells called cuvettes. These cuvettes are made up of
glass (for Visible) or Quartz (for UV).
These cuvettes are available in path lengths ranging from 1mm to 10cm.

4. Detector
After the light passed through the sample, the transmitted light has to be detected and measured. These detectors take the
energy from the light and convert into an electrical signal that can be amplified and recorded. These detectors work on the
principle of photoelectric effect.
Commonly used detectors are photocells, phototubes and photomultiplier tubes.

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5. Amplifier and Readout

The electrical signal detected by the detector is translated into a form that is easy to interpret. This can be done by
amplifiers, ammeters, potentiometers and photometric recorders.

Applications:
1. It is a technique that allows the determination of concentration of substances and therefore enabling to study the rate of
reactions and to determine the rate equation. It is extensively used in quantitative analysis of all the species that absorb UV
and Visible radiations.
2. In clinical chemistry, it is extensively used to study the enzyme kinetics.
3. It is used in dissolution testing of tablets and products in the pharmaceutical industry.
4. It is used in the quantification of DNA and Proteins / Enzymes activity in fields of genetics and biochemistry.
5. Used in the quality control in development and production of dyes, inks and paint industry.
6. Used in quantification of organic materials and heavy metals in fresh and agricultural waters in environmental and
agricultural fields.

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Unit – 3 – SPECTROSCOPY AND

MOLECULAR SWITCHES
LEARNING CONCEPT – 6-7
Infra – Red Spectroscopy – Introduction to Infra - Red Spectroscopy – Principle involved in Infra – Red
spectroscopy. Instrumentation (block diagram) – Applications of Infra – Red Spectroscopy.

INTRODUCTION
Infra means beyond and infrared i.e. beyond red region. It deals with the absorption of radiation in the infrared region of
the electromagnetic spectrum. Infrared spectroscopy is used in identification of functional groups in pure compounds.
INFRARED REGIONS
Infrared spectroscopy can be rationalized as the spectroscopy that deals with electromagnetic radiation of infrared
frequency. There are three well defined infrared regions; each of them has the potential to provide different information
a. Near infrared (12820-4000 cm-1): Poor in specific absorptions, consists of overtones and combination bands
resulting from vibrations in the mid-infrared region of the spectrum.
b. Mid-infrared (4000-400 cm-1): Provides structural information for most organic molecules.
c. Far Infrared (400-33 cm-1): Has been less investigated than the other two regions; however, it has been used with
inorganic molecules.
The low energies, typically encountered within the infrared region, are not sufficient to cause electronic transitions;
however, they are large enough to cause changes in the frequency and amplitude of molecular vibrations.

Region Wave length (λ) in µm Wave Number (ʋ) in cm-1 Frequency Range in Hz
Near IR 0.78 – 2.5 12800 – 4000 3.8 × 1014 – 1.2 × 1014
Middle IR 2.5 – 50 4000 – 200 1.2 × 1014 – 6 × 1012
Far IR 50 - 1000 200 – 10 6 × 1012 – 30 × 1011
Mostly used 2.5 - 15 4000 - 670 1.2 ×1014 – 2 × 1013

BASIC PRINCIPLE
Consider a molecule made up of two atoms m1and m2 (m1>m2) combined by a covalent bond, which acts like a spring in
between the two atoms. Due to the difference in their masses, they possess a natural frequency of vibration.

When the applied radiation frequency equal to the natural frequency of the molecule, then the molecule absorbs IR
radiation, causes a vibration between atoms in the molecules, resulting in the stretching of the bond.

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The absorption of IR radiations will bring a change in the dipole moment of the molecule. This increases the amplitude and
frequency of vibrations; thus, the absorbance value is recorded. For a molecule to absorb IR radiations, must possess net
dipole moment.

TYPES OF VIBRATIONS
IR vibrations are of two types
• Stretching vibration (Involves back and forth movement)
▪ Symmetrical stretching
▪ Asymmetrical stretching
• Bending vibrations (Involve change in bond angles)
▪ Scissoring
In plane vibration
▪ Rocking
▪ Twisting
▪ Wagging Out of plane vibration

SELECTION RULES
1. A molecule will absorb suitable radiation when its natural frequency of vibration matches with the frequency of
incident radiation (i.e. a net transfer of energy takes place and it results in a change in the amplitude of molecular
vibration)
2. A molecule will absorb IR radiation if the change in the vibrational state is associated with the change in the
dipole moment of the molecule.

INSTRUMENTATION

Basic components
a. Source
b. Monochromator
c. Sample holder
d. Detector
e. Readout
a. SOURCE
The common IR sources used are
i. Nernst glower: It employs a hollow rod of zirconium and yttrium heated up to 1500°C, emit the IR radiations
in the range 0.4 to 20 μm.
ii. Globar source: It consists a silicon carbide rod heated at 1200°C, emit radiation in the range 1 – 40 μm.
Globar source is more stable than the Nernst glower

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b. Monochromator
As the sample in IR spectroscopy absorbs in certain frequencies, it is necessary to select desired frequencies from
the radiation source. This can be achieved by two monochromators namely prism monochromator and grating
monochromator.

c. Sample holder
Solids, liquids and gases can be characterized using this technique. Gases are analyzed by tubes made up of glass.
Liquids are analyzed as films or solutions in NaCl or KCl tubes. Solids are analyzed as KBr pressed discs or as
suspensions.

d. Detector
Two types of detectors are used in Infra-red spectrophotometers
a). Thermal detectors: Thermocouple or bolometer
b). Photo conducting detectors or pyro electric detectors

e. Amplifier and Readout

Radiation detectors generate electronic signals which are proportional to the transmitted light. These signals are
transformed to IR spectra using a personal computer capable of handling Fourier transformations.

Infra-red Spectrum
It is a plot drawn between wavenumber on X – axis and
corresponding transmittance on y-axis.

APPLICATIONS
1. Used in the identification of functional group and structural
elucidation of an organic compound.
2. Used to compare between organic compounds.
3. Progress of chemical reaction can be determined by
examining the small portion of the reaction mixture
withdrawn from time to time.
4. IR spectrum can be used to determine the presence of impurities in the compound.

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Unit – 3 – SPECTROSCOPY AND

MOLECULAR SWITCHES
Introduction
LEARNING CONCEPT – 8 In the development of nanotechnology, nanoelectronic circuits and components
Molecular switches - NOR and NOT
play an essential role in developing smaller, faster, and more efficient devices.
logic gate operators - Characteristics
The traditional “top-down” approach in nanoelectronics, where the size is
of molecular motors and machines,
Rotaxanes and Catenanes as artificial reduced to 14 nm, is limited due to the failure of classical laws. The bottom-up
molecular machines. approach involves the construction of complex structures from the atomic level.
This enables the creation of highly sophisticated and precise components and
overcomes technological barriers.

What is a Molecular switch?

Molecular switches are single molecules capable of transitioning between two stable states in response to various stimuli
such as electric current, temperature changes, chemical environment or light.
The oldest form of synthetic molecular switches are pH indicators which exhibit different colors due to changes in pH of the
medium.

Molecular switches as Logic gate operators

These can be used to create tiny logic gates, like NOR and NOT gates, which are the building blocks of computers.

1. Molecular Switches as NOR Gate Operators:

Imagine two tiny switches, A and B. A NOR gate checks if either A or B is on. If either or both are on, the NOR gate turns
off the output. It's like a combined "not or" function. Molecular switches can work together to perform this function, making
them essential for building molecular-scale computers.
Example: Consider a molecule that has two photosensitive groups attached to it. When either of the two light wavelengths
(inputs) is present, the molecule switches to an "inactive" form (output = 0). However, if no light (neither input A nor input B)
is present, the molecule remains "active" (output = 1). This mimics the behavior of a NOR gate.

2. Molecular Switches as NOT Gate Operators:

Imagine a tiny switch that can be turned on or off. This molecular switch can change its shape when triggered by light or
other signals. If it's on, a NOT gate flips it off. If it's off, the NOT gate turns it on. It's like a tiny inverter, flipping the signal.
Example: In the presence of a specific input (say a chemical stimulus), the molecule could transition from a fluorescent state
(1) to a non-fluorescent state (0), or from a colored state to a colorless state.

Practical Applications:
• Molecular Computing: These molecular logic gates are seen as fundamental components for future molecular-
scale computers or data storage devices.
• Sensors: Molecular logic gates can be integrated into sensors that respond to specific environmental conditions
(pH, redox potential, etc.) and give a clear on/off output.
• Molecular Electronics: Molecular switches are crucial in developing nanoscale electronic devices such as
transistors, memory devices, and molecular diodes, which rely on switching behavior to encode and process
information.
• Smart Materials: Switchable materials can change their properties (e.g., color, conductivity, or mechanical
strength) in response to environmental stimuli, finding applications in adaptive clothing, responsive surfaces, and
coatings.

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• Drug Delivery: Molecular switches are used in targeted drug delivery systems where the drug is released in
response to specific stimuli (e.g., pH, light, or temperature) in the body, improving treatment efficacy and reducing
side effects.

Molecular motor
A motor is a device that consumes energy in one form and converts it into motion or mechanical work. Molecular motors
are specialized protein molecules that convert chemical energy to mechanical work within cells. They are critical for various
biological processes such as intercellular transport, cell division and muscle contraction.

Characteristics of molecular motors

Molecular motors are tiny, protein-based machines that power movement in cells. Here are their main characteristics in
simple terms:
1. Energy Efficient: They convert chemical energy (from ATP) into movement with high efficiency.
2. Move in One Direction: They usually move along cellular "tracks" in one set direction.
3. Step-by-Step Motion: They move in steps, taking small "jumps" with each ATP energy cycle.
4. Generate Force: They create a force to push or pull cellular cargo.
5. Carry Specific Cargo: They attach to specific items in the cell to transport them to the right place.
6. Need ATP: They rely on ATP as their main energy source.
7. Flexible Shape: They can change shape slightly to move around obstacles.
8. Controlled by Signals: They are regulated by signals in the cell, which turn them on or off.
9. Variable Speeds: Different motors move at different speeds based on their jobs.

Classification of Molecular motors

Molecular motors are of two types

• Naturally occurring molecular motors
• Synthetic rotary molecular motors

Naturally occurring molecular motors

These motors are found in nature and are primarily responsible for essential cellular functions. Examples include:
• Myosin: Found in muscles, it converts chemical energy from ATP into mechanical work, causing muscle contraction.
• Kinesin and dynein: These motors transport cargo within cells along microtubules, playing vital roles in cell division,
intracellular trafficking, and signaling.
• ATP synthase: Located in the mitochondria and chloroplasts, it uses the energy from proton gradients to synthesize
ATP, the primary energy currency of cells.
Functions: Intracellular transport, cell division, muscle contraction, ATP synthesis, DNA/RNA processing.
Energy Source: Mostly ATP or ion gradients.

Synthetic Rotary Molecular motors are

Synthetic rotary motors are human-made molecules designed to mimic the rotational movement seen in natural systems.
These motors typically use light, chemical reactions, or electric fields to power their rotation and are being developed for
applications in nanotechnology and materials science.
These are of 3 types
• Light-driven rotary molecular motors
• Chemically driven rotary molecular motors
• Electric or Magnetic field-driven rotary molecular motors

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While still in their early stages of development, synthetic molecular motors have potential applications in fields such as:
Nanotechnology: They could be used to build tiny machines for drug delivery, diagnostics, and materials science.
Electronics: Molecular motors could potentially power nanoscale devices and sensors.
Molecular computing: They might be used to develop new types of information processing and storage devices.

Rotaxane
A rotaxane is a mechanically interlocked molecule consisting of a dumbbell-shaped molecule threaded through a
macrocycle (ring-shaped molecule). The name "rotaxane" comes from the Latin words "Rota" (wheel) and "axis" (axle),
reflecting the ring-and-axle structure.
The dumbbell ends are bulky enough to prevent the ring from slipping off, making the structure kinetically stable.

Cyclobis (paraquat-p-phenylene) macrocycle.

Properties
Rotaxanes, due to their unique molecular architecture, possess a range of intriguing properties:

• Mechanical Properties: The rotaxanes have dynamic properties, with the ring able to move along the dumbbell
and exhibit kinetic stability as the bulky end groups on the dumbbell component prevent the ring from slipping off.
• Optical Properties: Rotaxanes exhibit nonlinear optical properties (Two-photon absorption, they can absorb two
photons simultaneously, leading to nonlinear optical effects like frequency doubling and optical limiting) and
photochromism (the reversible change of color upon exposure to light), making them suitable for optical materials
and devices.
• Electrochemical properties: Rotaxanes can exhibit redox activity, allowing for the control of the ring's position
through electrochemical stimuli. Certain rotaxanes can also exhibit conductive properties, making them potential
candidates for molecular electronics.
• Supramolecular Structures: Rotaxanes can self-assemble into complex supramolecular structures, leading to
materials with novel properties.

Applications
Due to their unique properties, rotaxanes have potential applications in various fields:
• Molecular Machines: Rotaxanes can be used as building blocks for molecular machines, such as molecular
motors and switches.
• Materials Science: Rotaxanes can be incorporated into materials to impart specific properties, such as
conductivity, nonlinear optical behavior, and self-healing capabilities.
• Sensors: Rotaxanes can be used as sensors for various analytes, such as ions and small molecules.
• Drug Delivery: Rotaxanes can be used as drug delivery vehicles, allowing for controlled release of therapeutic
agents.

DEPARTMENT OF CHEMISTRY 3
 MVGR COLLEGE OF ENGINEERING (AUTONOMOUS)

Catenanes
A catenane is a mechanically interlocked molecule composed of two or more interlinked rings. These rings are not
chemically bonded but are mechanically interlocked, meaning they cannot be separated without breaking a covalent
bond.

Properties
Catenanes, due to their unique interlocked structure, possess several interesting properties:
• Mechanical Bond: The rings in a catenane are locked together like links in a chain, and they cannot be separated
without breaking the chain.
• Ring Rotation: The rings in a catenane can rotate relative to each other, leading to dynamic properties.
• Molecular Recognition: Catenanes are designed to incorporate molecular recognition sites, allowing them to bind
to specific molecules or ions.
• Self-Assembly: Catenanes can self-assemble into complex supramolecular structures.
• Topological Chirality: Some catenanes can exhibit topological chirality, meaning they can exist in two non-
superimposable mirror-image forms.

Applications
• Molecular Machines: Catenanes can be used as building blocks for molecular machines due to their ability to
undergo controlled mechanical motions.
• Sensors: Catenanes can be designed to act as sensors for specific molecules or ions, as their properties can
change upon binding to target analytes.
• Materials Science: Catenanes can be incorporated into materials to impart unique properties, such as enhanced
mechanical strength, conductivity, or nonlinear optical behavior.
• Drug Delivery: Catenanes can be used as drug delivery vehicles, allowing for controlled release of therapeutic
agents.

DEPARTMENT OF CHEMISTRY 4