1

Exploring the Effect of Altering the Donor Fragment

on ΔEST and λem of TPA-DCPP Based Derivatives.
A DFT Study

A Thesis submitted to

University of the Punjab

In the partial fulfillment of requirement for the degree of

BS in Chemistry

BY
KHADIJA ISHTIAQ
Roll # 19
SESSION: 2021-2023

SCHOOL OF CHEMISTRY
UNIVERSITY OF THE PUNJAB, LAHORE
 2

APPROVAL CERTIFICATE

It is declared that the research work reported in this thesis entitled “Theoretical Investigations
of Thermally Activated Delayed Fluorescence (TADF) Materials via H/NO 2 Substitution at
Diphenylsulphone Acceptor” has been performed by KHADIJA IAHTIAQ, Roll No. 19,
student of BS Chemistry (ADP-M), University of the Punjab, Lahore, session 2021-2023, under
my supervision for the partial fulfillment of requirement for the degree of BS in Chemistry.

Supervisor
Prof. Dr. Farah Kanwal
Professor
Centre for Physical Chemistry
School of Chemistry
University of Punjab, Lahore

Co-Supervisor
Dr. Aftab Hussain
Assistant Professor
Centre for Physical Chemistry
School of Chemistry
University of Punjab, Lahore
 3

DEDICATION

This work is dedicated to

My Parents ISHTIAQ AHMAD and FATIMA ISHTIAQ

And my Brother ABU BAKER ISHTIAQ

Who always supported me in every decision of mine and had always been a source of inspiration
for me.
 4

ACKNOWLEDGEMENT

All praises be to ALMIGHTY ALLAH, the Lord of the world, the Master of the Day, WHO
always show blessings upon me and enables me to gain knowledge in my research work. Without
HIS mercy and grace, this work would not have been accomplished. All respect to the HOLY
PROPHET MUHAMMAD (PBUH) for a comprehensive and everlasting source of guidance
and knowledge for humans.

I am very thankful to my supervisor Prof. Dr. FARAH KANWAL, School of Chemistry,

University of the Punjab, and my Co-supervisor Dr. AFTAB HUSSAIN (Assistant Professor)
School of Chemistry, University of the Punjab for their generous provision and continuous
encouragement throughout my work. I am also thankful to Prof. Dr. MUHAMMAD ABDUL
QADIR, Director of the School of Chemistry, for providing me all facilities for the completion
of my research work.

Special thanks to my Father ISHTIAQ AHMAD, my brother ABU BAKER and my WHOLE
CLASS for their constant support and sincere prayers.

KHADIJA ISHTIAQ
 5

ABSTRACT
So far, thermally activated delayed fluorescence (TADF) materials of red, blue, and green colors
are often used in highly-proficient organic light-emitting diodes (OLEDs). However, because of
the difficulties in molecular design, effective TADF materials with a color varying from red to
near-infrared (NIR) color are infrequently described. Herein, we are going to present a
theoretical investigation of the singlet-triplet energy gap (ΔEST) and emission wavelength (λem) of
red to NIR-TADF materials via structural modification of the donor fragments on the parent
molecule Triphenylamine dicyanopyrazino Phenanthrene (TPA-DCPP). The incorporation of
different donor fragments like Dimethylacridine (DMAC), phenoxazine (PXZ), and
carbazole (CZ) with various electron-donating strengths has been investigated employing density
functional theory (DFT) and time-dependent density functional theory (TD-DFT) at M06/6-31G*
theoretical level. It can be seen that the highest occupied molecular orbitals (HOMOs) and
lowest un-occupied molecular orbitals (LUMOs) are residing on donor (D) and Acceptor (A)
parts of the molecules, respectively. The investigated molecules PXZ-DCPP and DMAC-DCPP
are showing lower values of HOMO-LUMO overlap (ρ) and hence lower values of ΔEST while
CZ-DCPP shows a higher value of ρ and ΔEST than parent molecule TPA-DCPP. It is noted that
the ΔEST values decrease with the increase in the electron-donating strength of the donor moieties
in the order of DMAC < PXZ < TPA < CZ. The absorption and emission wavelength (λab and
λem) values lie in the range of 469-628 nm and 522-774 nm respectively. It is perceived that the
designed molecules PXZ-DCPP and DMAC-DCPP are showing a bathochromic-shift while
CZ-DCPP exhibits a hypsochromic-shift compared with the parent molecule. Among all the
investigated materials DMAC-DCPP and PXZ-DCPP with a lower value of ΔEST (0.0001,
0.0005 eV) and emission wavelength in the region of (651 and 774 nm) are considered the best
candidate for red to NIR-TADF materials. We hope our theoretical investigation might offer
hints for the production of highly-efficient red to NIR-TADF-OLEDs in the future.

Keywords: Thermally activated delayed fluorescence (TADF), structural modification, TPA-

DCPP, DFT, TD-DFT, HOMO-LUMO, OLED, Singlet Triplet energy gap (ΔEST).
 6

TABLE OF CONTENTS
Abstract………………………………………………………………………….
Chapter 1: INTRODUCTION
1.1 History……………………………………………………………………
1.2 Light emitting diodes (LED)
1.3 Organic light emitting diode (OLEDs)……………………………………
1.3.1 Construction of OLED……………………………………………………….
1.3.2 Working of OLEDs………………………………………………………
1.3.3 Fluorescent Emitters…………………………………………………. …..
1.3.4. Phosphorescent Emitters…………………………………………………
1.4 Thermally Activated Delayed Phosphorescent materials (TADF)……………………
1.4.1 Mechanism of TADF Materials:
1.5 Factors Effecting the Efficiency
1.5.1 Singlet-Triplet Energy Splitting:
1.5.2 Effect of Temperature:
1.5.3 Color of TADF emitters:
1.6 Design Principle of TADF Molecule
1.6.1 Donor Moieties:
1.6.2 Accepter Moieties:
1.6.3 By small TADF molecules
1.6.4 By Linker
1.7 Recent Days Developments:
1.8 Future Challenges of TADF Mechanism
Chapter 2: LITERATURE REVIEW…………
Chapter 3: COMPUTATIONAL METHDOLOGY:
3.1 Computational Details
3.2 Density Functional Theory (DFT)
3.2.1 Recent Advances
3.3 Time Dependent Density Functional Theory
3.4 Hartree- Fock Theory
3.5 Schrodinger Wave Equation
 7

3.6 Absorption Spectra

3.6.1 σ-σ * Transition
3.6.2 n-σ* Transition
3.6.3 π-π * transition
3.6.4 n-π* Transition
Chapter 4: RESULTS AND DISCUSSION
4.1 Functional Analysis:
4.2 The ΔEST
4.3 Frontier Molecular Orbitals:
4.4 Photophysical Properties:
4.5 CONCLUSION
Chapter 5: REFERENCE
 8

Chapter 1
INTRODUTION
HISTORY:
In ancient times, humans lived without modern comforts, relying on animals and plants for
sustenance and using plant leaves as clothing. As time passed, humans acquired knowledge and
skills, learning to build houses, make clothes, and cook food. This led to a curiosity about nature,
eventually leading to the groundbreaking discovery of electricity. The invention of electricity
sparked the interest of scientists who went on to identify three types of materials: conductors,
insulators, and semi-conductors [1]. Conductors allow electricity to flow easily due to
overlapping energy bands, while insulators have a large energy gap that prevents the flow of
electrons. Semi-conductors have a smaller energy gap and became a fascinating subject for
scientific exploration.

Figure 1 The energy gap between conductor, insulators and semi-conductors

Various electronic devices have been created by incorporating doped semiconductors. One of the
notable inventions “incandescent light” bulb was by Thomas Edison’s in 1879. The light bulb
operates by passing an electric current through its filament. As the current reaches a certain level
the filament gets heated up and emits light. In Edison's incandescent light bulb, electricity makes
the filament hot, and then it gives off light. It converts electrical energy into heat energy and then
into light energy. In 1962, Nick Holonyak invented the first LED.
 9

LED (light emitting diode):

An LED directly converts electrical energy into light energy. Light Emitting Diode (LED) [2]
consists of three layers:
• p-type semiconductor,
• n-type semiconductor
• depletion layer.
The p-type semiconductor and the n-type semiconductor are separated by a depletion region or
depletion layer. and when electricity flows through it light is produced. LEDs only work when
the electricity flows in a specific direction. When this happens electrons and holes combine and
releasing light energy.

Figure 2 Working principle of OLED

OLED (organic light emitting diodes):

OLED: An organic light-emitting diode (OLED) [3] is a special type of electronic device made
of a thin layer of carbon-based material that produces light when electricity is applied. It needs at
least one transparent electrode for the light to come out. The idea of using organic materials for
this purpose has been around for almost 50 years but the first effective thin film OLED was
created in 1987 by Tang and Van Slyke.
 10

• Single-Layer OLED
• Multilayer-Layer OLED
Single-Layer OLED:
A simpler version of OLED called the single-layer OLED became popular because of its easier
manufacturing process and design. However, it had some issues with unbalanced charges,
making it less effective.
Multilayer-Layer OLED:
To solve this problem, multilayer OLEDs were developed. These modern OLED devices have
multiple organic layers between two electrodes to balance the charges better, but they still work
based on the same fundamental principle. In multilayer OLEDs, they add more organic layers to
make the device work better. These extra layers help to balance the electric charges and allow the
light-producing zone to be in the middle of the device.
Basic structure of an OLED:
The basic structure [4] of an OLED cell includes different layers:
1. Substrate: The foundation of the OLED, it can be made of plastic, glass, or metal foil.
2. Anode: This can be a transparent material called ITO or not, depending on the type of OLED.
It has a positive charge and injects holes into the organic layers of the OLED
3. Hole Injection Layer (HIL): It sits on top of the anode and receives holes from the anode,
guiding them deeper into the OLED.
4. Hole Transport Layer (HTL): This layer helps holes move across it, allowing them to reach
the emissive layer, and it contains special materials that can form stable cation radicals.
5. Emissive Layer: The heart of the device where light is produced. It consists of a color
defining emitter mixed into a host material. This is where electrical energy becomes light.
6. Blocking Layer (BL): Used to improve OLED technology by keeping charge carriers
confined to the emissive layer.
7. Electron Transport Layer (ETL): It helps electrons move across it to reach the emissive
layer.
8. Cathode: This can be transparent or not, depending on the type of OLED. It has a negative
charge and injects electrons into the organic layers of the OLED. Metal materials with low work
function are used as cathodes.
 11

Fig 3: Construction of OLED

Working Of OLED:
OLEDs work [5] by exciting electrons with applied voltages. When these electrons return to
their normal state, they release energy in the form of light. In OLEDs, there are singlet and triplet
excitons, with a ratio of 25% to 75%. To make use of all excitons, three generations of emitters
have been developed.
Fluorescence Emitters:
The first-generation emitters are also known as fluorescence emitters [6]. Fluorescence is a
process where light is emitted when electrons transition from the first excited state to the ground
state without changing their spin. In this process, only 25% of singlet excitons are used to emit
light. The second-generation emitters are also known as phosphorescence emitters.
Phosphorescence Emitters:
Phosphorescence [7] is a process where light is emitted when electrons transition from the first
excited triplet state to the ground state, with a change in spin. It's slower than fluorescence. In
phosphorescence, 100% of excitons are used to emit light through a process called inter-system
crossing. However, using phosphorescence in OLEDs involves the use of heavy metals, which
are harmful to the environment and toxic. To reduce the reliance on these heavy metals, a new
type of emitters called TADF emitters [8] has been developed.
 12

TADF (Thermally activated Delayed Fluorescence diode):

TADF (Thermally Activated Delayed Fluorescence) [9] was first observed in an organic
molecule called eosin by Parker and Hatchard in 1961. They noticed delayed fluorescence
from the same excited state as the prompt fluorescence, along with phosphorescence. In 1980,
Blasse and colleagues discovered the first metal-containing TADF material using a Cu (I)-
complex. In the late 1990s, Berberan-Santos and colleagues confirmed effective delayed
fluorescence in fullerenes, which was then used for temperature and oxygen sensing. In 2009,
attempts were made to use TADF materials in OLEDs, and in 2012, Adachi et al. proposed a
TADF mechanism for purely blue organic compounds with high efficiency. By adopting the
Donor-Acceptor strategy, they achieved nearly 100% EL (electroluminescence) efficiency and a
small energy difference between the excited states. In 2014, Adachi et al. reported a blue TADF
OLED [10] with an EQE (external quantum efficiency) of 19.5%. The Adachi group developed
new OLEDs using advanced TADF technology, which improves upon previous generations while
keeping their advantages. These OLEDs can use both singlet and triplet excitons to emit light,
potentially achieving 100% internal quantum efficiency. TADF materials have many benefits
compared to other OLED materials, like high efficiency, no heavy metal doping, and no
shortages of conventional materials. TADF is a fascinating technique for harvesting triplet states
in metal-free organic materials for use in OLEDs, converting non-emissive triplet states into
emissive singlet states.

Mechanism:
In TADF emitter-based OLEDs, both the singlet and triplet excitons are used by a process called
reverse intersystem crossing [11]. The small energy gap between the first excited triplet and
singlet states (ΔEST) is important factor for TADF emitters. When this gap is small, electrons
can efficiently convert from the triplet to the singlet state, achieving 100% internal quantum
efficiency [12]. TADF emitter-based OLEDs are environmentally friendly and reduce the need
for heavy-metal-based phosphorescence OLEDs. Currently, a lot of research is focused on
improving the efficiency of TADF emitters. Several factors influence their efficiency.
 13

Fig 4: Mechanism of TADF

ISC:
Intersystem crossing (ISC) is a vital part of the TADF process. It's a non-radiative, adiabatic
process that happens between different types of energy states, like singlets and triplets. For
example, ISC [13] from the first singlet excited state (S1) can occur from its zero-point
vibrational level or from higher vibrational levels due to heat. This process involves transitions
between closely matched triplet states, such as excited vibrational levels of T1 or other higher
excited states (Tn). Intersystem crossing is usually not allowed according to quantum mechanics
rules.
RISC:
Usually, RISC [14] happens from the lowest excited triplet state (T1) to the lowest excited
singlet state (S1) in a molecule. Materials with efficient RISC can be used to increase the
efficiency of fluorescent organic light-emitting diodes by utilizing both singlet and triplet
excitons formed in the device. To achieve efficient RISC, the rate of RISC (kRISC) must be
higher than the rate of non-radiative triplet pathways. Efficient TADF molecules need to have a
small energy gap (ΔEST) [15] between the singlet and triplet excited states and minimize non-
radiative decay to allow the triplet excited state to live long enough for effective triplet
harvesting through the thermally activated reverse intersystem crossing mechanism (RISC),
which maximizes the fluorescence yield. The equation (1.1) shows that a small ΔEST is crucial
 14

to maximize the RISC rate constant (kRISC), so understanding how to minimize it in molecular
structures is essential.
Factors effecting the Efficiency:
• Singlet-Triplet Energy Splitting
• Temperature
• Color Of TADF Emitter
Singlet-Triplet Energy Splitting:
The main factor is the small energy gap (ΔEST) [15,16] between the first excited singlet and
triplet states (T1). When this gap is small, electrons can efficiently move from the triplet to the
singlet state through reverse intersystem crossing, making the TADF emitter more efficient.
TADF stops happening when the singlet-triplet energy gap is above 0.2 eV. So, light-emitting
molecules with a ΔEST value below 0.2 eV can undergo reverse intersystem crossing (RISC).
Typically, the energy gap in light-emitting molecules is in the range of 0.5-1.0. To reduce the
singlet-triplet energy gap, the exchange integral between singlet and triplet excitons needs to be
minimized, achieved by spatially separating highly occupied molecular orbitals (HOMO) and
lowest unoccupied molecular orbitals (LUMO) in the donor and acceptor parts of the molecule,
respectively.
Effect of Temperature On TADF:
The temperature also affects TADF efficiency. High temperatures favor the reverse intersystem
crossing process, as a low energy gap between S1 and T1 occurs at high temperatures, leading to
greater TADF efficiency.
Color of TADF Emitter:
The color [17] of the TADF emitter depends on the donor and acceptor moieties used. These
moieties determine the energy levels called HOMO and LUMO. The color is determined by the
energy difference between these levels. A bandgap of 2.8 eV (450 nm) results in a blue color,
while a bandgap of 1.9 eV (650 nm) produces a red color.

MOLECULAR DESIGN PRINCIPLES:

The design of TADF emitters relies on donor and acceptor moieties. Their arrangement and ratio
are crucial. There are several methods to design TADF emitters:
 15

1. The multi-donor method is commonly used, where the donor and acceptor are combined in
ratios ranging from 1:1 to 4:1.
2. Another method involves connecting two small TADF emitters using a single bond between
their acceptors, creating a larger TADF emitter.
3. Adding a linker between the donor and acceptor is another approach to design TADF emitters.
DONOR-ACCEPTOR MOLECULES:
In simple words, the donor-acceptor molecular framework [18] is a strategy used to make
OLEDs (organic light-emitting diodes) more cost-effective. It involves arranging certain
molecules in a way that separates their electron donating and withdrawing parts. By doing this,
the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals
(LUMO) are kept apart, which reduces energy overlap and results in lower costs. This
framework allows for the creation of metal-free molecules suitable for OLEDs. Additionally, by
incorporating both donor and acceptor groups within the same molecule, it reduces the number
of layers needed. Different combinations of donor and acceptor groups are designed to enhance
charge transfer in these OLED materials.
• Acceptor Moieties
• Donor Moieties
Acceptor Moieties:
The accepter moieties [19] are functional groups that have a deficiency of electrons and a
relatively deep lowest unoccupied molecular orbital (LUMO), which makes it possible for them
to participate in the transport of electrons and be easily reduced.
Donor Moieties
The donor moieties [20] are functional groups having an excess of electrons and a relatively deep
highly occupied molecular orbital (HOMO), which makes it possible for them to participate in
the transport of holes and be easily oxidized. In TADF emitters, major donor moieties are amine
type (diphenylamine) and carbazole-type molecules. Some donors are thianthrene, phenazine,
phenoxazine, phenothiazine, and Dimethylacridine.
 16

Figure 5: structure of Donor and Acceptor that used in TADF material

Thermally Activated Delayed Fluorescence (TADF) molecule from small TADF molecules:
Select small molecules that exhibit TADF properties, which means they can efficiently harvest
both singlet and triplet excitons. Understand the key factors contributing to TADF, such as the
energy levels of the singlet and triplet states and the efficiency of the reverse intersystem
crossing (RISC) process. Modify the selected small TADF molecules through chemical synthesis
or structural modifications to enhance their TADF efficiency. This can be achieved by adjusting
the molecular geometry, introducing electron-donating or electron-accepting groups, or
optimizing the energy levels of singlet and triplet states Use spectroscopic and photophysical
techniques to characterize the newly designed molecules and confirm their TADF behavior. If
the goal is to use the TADF molecule [21] in organic light-emitting diodes (OLEDs) or other
optoelectronic devices, incorporate the designed TADF molecules into the device architecture
and evaluate their performance.

Design TADF material by linker:

 17

Designing a Thermally Activated Delayed Fluorescence (TADF) material with the help of a
linker involves using a bridging unit to connect two or more small TADF molecules. This
approach can create a larger and more complex TADF material with enhanced properties. Here
are the steps to design a TADF material using a linker [22]:
1. Identify suitable TADF molecules: Start by selecting small TADF molecules that exhibit
efficient TADF properties and can serve as building blocks for the linker design.
2. Choose a suitable linker: Select a bridging unit (linker) that can connect the chosen TADF
molecules while preserving their TADF properties. The linker should have appropriate energy
levels and structural compatibility with the TADF units.
3. Design the TADF material: Connect the TADF molecules using the chosen linker through
chemical synthesis. The linker should be strategically placed to facilitate efficient energy transfer
and charge transfer processes between the TADF units.
4. Analyze the TADF mechanism: Understand how the presence of the linker affects the energy
levels of the singlet and triplet states and influences the reverse intersystem crossing (RISC)
process.
5. Characterization: Use spectroscopic and photophysical techniques to characterize the newly
designed TADF material and confirm its TADF behavior. Assess the emission properties and
efficiency of the material.
6. Device fabrication: If the goal is to use the TADF material in optoelectronic devices,
incorporate it into the device architecture and evaluate its performance [23]. This may include
OLEDs, organic photovoltaics (OPVs), or other TADF-based applications. 7. Optimization:
Continue iterative optimization to enhance the TADF efficiency and stability of the designed
material for practical applications. It's essential to conduct thorough theoretical and experimental
studies to optimize the TADF material's properties and performance. Additionally, collaboration
with experts in organic chemistry and materials science can be beneficial for successful TADF
material design using a linker approach. As TADF research is continually evolving, stay updated
with the latest literature and advancements in the field.

Recent developments.
 18

TADF-OLEDs are now present in numerous households, offices, and various locations. A wide
range of these substances is accessible in the market. TADF materials unquestionably belong to
the most encouraging material categories that will help address current challenges with OLED
devices. Presently, OLEDs are employed for displays in diverse devices like computers, TVs,
military vehicles, LCD screens, mobile phones, and MP3 players. Semi-conductor materials
continue to be the main focus of researchers

FUTURE CHALLENGES:

Although TADF emitters are among the bests we have we still need to enhance some properties
and improve some parameters to make them more efficient. There are some future challenges to
TADF emitters:
1- We still need to decrease the energy separation between the first excited singlet and to excited
triplet to increase the reverse intersystem crossing and hence to increase the efficiency of the
material.
2- We still need to get the high emission efficiency and low decay lifetime of the excited state
simultaneously.
Different techniques or methods can be employed to complete these challenges [24]. Some
of them are as follows:
1. We can replace the donor of the TADF emitter with a donor which has a high tendency to
electrons donating.
2. Similarly, we can also replace the acceptor moiety.
3. Third and most important method is adding a linker or spacer or pi- the bridge between
the donor and acceptor moieties to enhance the efficiency of the TADF emitter.
In this work, we have replaced the donor fragment of Triphenylamine dicyanopyrazino
Phenanthrene (TPA-DCPP) with a donor having better electron donating tendency and take a
theoretical investigation of ΔEST and λem value. The Triphenylamine (TPA) donor has been
substituted with the donors such as phenoxazine (PXZ), carbazole (CZ), TPA-tBu, PXZ-tBu),
and CZ-tBu. The parent molecule and Scheme of study is shown in Figure 1. The designed
molecules are shown in figure 2.

a
 19

Figure 1. (a) Parent Molecules, (b) Scheme of study

 20

Figure 2. Designed Molecules

 21

Chapter 2
Literature Review:
C.A. Parker, 1961, Eosin showed phosphorescence and delayed fluorescence emission bands in
ethanol at the temperature of 70C.Eosin glowed and emitted light in ethanol at 70 degrees
Celsius. Scientists calculated the factors for a specific type of light transition, as well as the
efficiency of creating certain light states and the energy needed for the process. They also found
approximate rates for three different light transitions. There's some indication of light transitions
happening at a higher vibrational level of the excited state [25].
S.A. VanSlyke, 1987, The electroluminescent device had three parts: an organic hole injecting
and transporting zone, an organic electron injecting and transporting zone, and a cathode. The
hole injecting and transporting zone consists of two layers: one in contact with the anode
containing a compound that injects holes, and another layer between the hole injecting layer and
the electron injecting and transporting zone containing a hole-transporting aromatic tertiary
amine [26].
Jing Lu, 2015, Researchers used density functional theory and time-dependent density
functional theory to study thermally triggered delayed fluorescent compounds based on benzo
[1,2-b:4,5-b0]dithiophene. Theoretical calculations showed that the proposed molecules with
substitutions in the 4, 8-positions had a combination of charge transfer and locally excited
components. These compounds were predicted to emit light at long wavelengths. The expected
mobility of holes and electrons for the proposed 4, 8-positions substituted molecule with specific
electron-accepting units was 3.43 and 0.18, respectively, and it had no energy gap between its
singlet and triplet states [27].
Yan Liu, 2020, To make a new material called t3Cz-SO, tert-butyl carbazole was added to the
edges of the original TADF units. The t3Cz-SO material has estimated energy levels that allow it
to efficiently emit light. It can form films well and remains stable in shape, making it suitable for
making OLEDs through solution-based processes. When compared to the original TADF
material without changes, the device using t3Cz-SO as a host with FIrpic achieved a low starting
voltage of 3.5V and a high-power efficiency of 16.5. This research shows that adding tert-butyl
carbazole to the TADF emitter can effectively create electroluminescent materials[28] .
Bidhan Chandra Garain, 2020, Scientists used a boron-based organic material that glows after
some time when heated to study how it absorbs and releases light. The material has separated
 22

parts that control the flow of electricity, and it undergoes charge transfer when absorbing light.
The excited states of the material have specific patterns of localized electrons and holes. When
the distance between two of these excited states is reduced, the reverse process of absorbing light
becomes efficient [29].
Xue-Qi Wang, 2020, Two new 3D glowing materials, DM-BD1 and DM-BD2, were made using
special patterns of charged parts and light-absorbing components. These patterns allowed
efficient interactions between the charged parts, resulting in high glowing brightness of 94.2%
and 92.8% for the two materials. These materials also showed quick light-absorbing and light
releasing processes. Devices made with DM-BD1 and DM-BD2 achieved very high brightness
levels of 28.0% and 26.6%, respectively, which were better than other similar materials.
Ki Joon Yang, 2021, Researchers conducted a detailed study to find out why the efficiency of
mDABNA based TADF devices varies when different host materials are used. They found that
adding peripheral diphenylamine extensions to the m-DABNA molecule prevented the transfer
of energy from the host material. Instead, the energy stayed mostly in the core region of
mDABNA. As a result, when wide band gap host materials were used, the devices showed good
efficiency with the help of a trap aided emission mechanism. This research helps us better
understand why OLED devices using the m-DABNA platform may have different efficiency
levels [30].
Jun-Ling Jin, 2021, Three glowing materials were created and studied, each containing an
Nphenylphthalimide acceptor and different electron-donating parts connected by an Ortho
phenyl linker. The folded structure of these materials created distinct regions for holding and
releasing electricity. For AI-Dps, AI-Pxz, and AI-Dmac, they had a small difference in energy
levels between the states that hold and release light. These materials showed a mix of two light
absorbing processes in one of their excited states, making them promising for efficient glowing
while keeping high brightness levels [31].
Sanja j. Armakovic, 2022, To check if three chemical structures could be used in organic
electronics, scientists studied them using computer simulations and calculations. They looked at
properties like charge transfer rates, mobility, and photovoltaic abilities. They also checked if the
materials could emit light with a delay when heated. The molecule modified with acridone
showed the best charge movement ability, comparable to the well-known pentacene molecule
[32].
 23

Chihaya Adachi et al, (2001), Using a special glowing chemical mixed into a material that has a
big energy gap, we can make really efficient organic light-emitting devices. We got really good
results with a chemical called bis (2-phenylpyridine) iridium (III) acetylacetonate
[(ppy)2Ir(acac)] mixed into another substance. It gave us bright light with high efficiency. This
works well because the light doesn't get lost as heat, and the different parts of the device work
together nicely [33].
Jiaoyun Wang et al, (March 2022), A special glowing material that changes color when it
detects a substance called fluoride ion. Scientists made this material by combining two different
molecules. By adding some parts to one of the molecules, they made it very good at detecting
fluoride ions. When fluoride ions are present, the material glows in a deep blue color instead of
green, and this change in color can help scientists detect fluoride ions even at very low amounts.
This material is very good at only detecting fluoride ions and can do it over and over again,
which makes it really useful for detecting fluoride [34].
Long Jiang et al, (April 2022), Researchers have developed a simple method to create special
molecules containing boron and carbon rings. These molecules have unique properties that make
them useful for making electronic devices. The researchers made five different versions of these
molecules and found that two of them could be changed into slightly different molecules by
reacting with oxygen. These molecules absorb and emit light in a way that's different from
similar molecules. Additionally, some of these molecules emit light more strongly when they are
clumped together. This discovery could be important for creating new materials for electronic
devices [35].
Sirui Yang et al, (Jan 2022), Understanding How Electrons Move in Certain Materials. When
light interacts with materials, the movement of charged particles (electrons) is important.
Researchers used two molecules, one giving electrons (donor) and the other receiving (acceptor),
connected by bridges. They found that the way electrons move within these molecules depends
on their structure. Longer bridges led to slower electron movement and longer electron life,
while when the molecules were made into a thin layer, the movement got faster again. This study
shows how to control the movement of electrons in these materials by changing their shape [36].
Qi OU et al, (Oct 2021), Making Light-Emitting Materials Shine Brighter. Besides the usual
process where different energy levels interact, we've found another way to make molecules emit
light more effectively. When certain molecules are in a cavity, their excited states can join forces
 24

with the cavity's own properties to speed up the process of emitting light. This works even for
molecules that aren't usually good at emitting light. By understanding and using this effect, we
can create new materials that are better at giving off light, which has potential uses in lighting
and technology [37].
Yan Li et al., (Dec 2011), Studying How Different Chemicals Glow. We're looking into how
certain chemicals can light up when used in devices like OLEDs. We tested a bunch of chemicals
and found that some make it easier for electricity to move through them. Adding specific groups
to the chemicals can either help with electron movement or hole movement (spaces where
electrons were). Changing the structure of the chemicals also affects how well they can light up
and how they carry electricity. This helps us design better materials for things like light-emitting
screens [38].
Begoña Milián-Medina et al., (Mar 2012) Creating Better Organic Materials for Brighter
Lights. We're working on making organic materials that give off bright light in devices like
OLEDs. We found that by using certain types of molecules with small energy gaps between
different states, we can improve the efficiency of organic LEDs and even make better solar cells.
However, we don't have clear guidelines yet for designing these materials. In our study, we used
computer calculations to design molecules with the right energy levels. These molecules have
very small energy gaps, which means they can produce light efficiently. For OLEDs, we also
need materials that don't lose energy easily, so we're looking for molecules with large energy
gaps [39].
Ye Tao et al., (2014), Exploring Special Materials for Better Electronics. Scientists are working
on creating new materials that can improve electronic devices. These materials have a unique
property where they can efficiently switch between different energy states when light interacts
with them. This allows them to produce light more effectively, which is useful for making
devices like organic light-emitting diodes (OLEDs), sensors, and other electronic gadgets. These
new materials perform really well, similar to expensive rare-metal compounds. Researchers are
studying different types of these materials, such as those made with metal-organic compounds,
molecules that have a special structure, and even fullerenes. By overcoming challenges and
understanding these materials, we could revolutionize the field of electronics [40].
 25

Aftab Hussain et al., (2019), Performed theoretical research on how CH/N and H/CN
substitution at the diphenyl-sulphone acceptor can be used to make TADF materials that range
from sky blue to blue. Based on 10,10-dimethyl-5,10-dihydro-pyrido[4,3-b] [1,6] naphthyridine–
diphenyl-sulphone (DMDHNP-DPS), a set of derivatives called 1a were made with CH/N and
H/CN substitutions at the DPS acceptor unit to make blue thermally activated delayed
fluorescence (TADF) materials. After changing the CH/N at the DMAC donor fragment, we
picked the parent molecule 1a from our previous report. The highest occupied molecular orbitals
(HOMOs) and lowest unoccupied molecular orbitals (LUMOs) were mostly spread over the
DMDHNP donor and DPS acceptor 28 units, respectively. This led to a slight overlap between
the HOMO and LUMO, which made the singlet–triplet energy gap (EST) smaller. Calculations
showed that the EST values of H/CN-substituted derivatives were smaller than those of the
corresponding CH/N derivatives. This was good for the reverse intersystem crossing (RISC)
process from the lowest excited triplet states (T1) to the lowest excited singlet states (S1) and
then to the ground state (S0), which caused delayed emission. All of the proposed molecules
were found to have emission wavelengths (em) between 397 and 497 nm. When the –NQ atom
or the –CN group was added to the ortho or meta position of DPA, the energy of the transition
from LUMO to HOMO in the S1 states went down. This caused a red-shift. Also, the em values
showed a bigger bathochromic change as the number of –NQ or –CN atoms or groups went up.
Two of the designed molecules (1h and 1i) showed sky-blue emission (494 nm and 497 nm), and
four of the investigated compounds (1c, 1d, 1f, and 1g) showed blue emission (416 nm, 447 nm,
437 nm, and 432 nm, respectively). This showed that these investigated derivatives were good
sky-blue to blue TADF candidates. Out of all the studied derivatives, the designed systems 1f
(0.03 eV) and 1g (0.02 eV) have the best chances of becoming blue TADF materials because
their EST values are smaller (0.03 eV and 0.02 eV, respectively) and their em values are close to
437 nm and 432 nm. Their theoretical research could give hints about how to make blue TADF-
based organic light emitting diodes (OLEDs) that work well in the future [41]
 26

Chapter 3

COMPUTATIONAL METHDOLOGY:
Computational chemistry, also called molecular modeling, uses computer technology to study
tiny molecules. It helps us understand how molecules look, act, and react. Many computer
programs have been created to do this. These programs make it easier to study molecules and
chemical reactions without needing to do dangerous experiments. The CMS society is planning
to improve these programs even more. This will help scientists design new molecules and study
chemical processes better. Unlike experiments, which have limitations, computational chemistry
can simulate many things quickly and safely. This makes it useful for studying new molecules
and reactions without the challenges of real experiments.
COMPUTATIONAL DETAILS:
The structures built using the Gaussview 06 were optimized using Gaussian 09 software at the
School of Chemistry, University of Punjab Lahore Pakistan. All the newly developed molecules'
configurations were computationally optimized using DFT employing the 6-31G* basis set and
the M06 functional. Using the PCM model, the influence of solvent was investigated. The
ground state and excited state geometry optimization was performed via DFT and TD-DFT. We
examined the HOMO-LUMO distribution [42] and HOMO-LUMO energy gap based on ground
state geometry. We also calculated the excitation energy and absorption wavelength. Then we
calculated the fluorescence and phosphorescence wavelength based on excited state geometry.
The Singlet-triplet energy gap and binding energy were also calculated from these files. Charge
injection and transport analysis was performed at the end to calculate the Reorganization of Hole
and electron
RECENT ADVANCES
Computational chemistry, also called molecular modeling [44], uses computer technology to
study tiny molecules. It helps us understand how molecules look, act, and react. Many computer
programs have been created to do this. These programs make it easier to study molecules and
chemical reactions without needing to do dangerous experiments. The CMS society is planning
to improve these programs even more. This will help scientists design new molecules and study
chemical processes better. Unlike experiments, which have limitations, computational chemistry
 27

can simulate many things quickly and safely. This makes it useful for studying new molecules
and reactions without the challenges of real experiments.

DENSITY FUNCTIONAL THEORY (DFT)

Initiating calculations about the structure of atoms, crystals, and molecules, as well as surface
analysis and interactions, are frequently done using density functional theory. DFT [44] has been
used in many areas of physics, but nowhere has it been more successfully than in solid-state
physics. It started out being employed in particle physics and has since moved to other fields
such as solid-state chemistry, materials science, mineralogy, high-pressure physics, and others,
allowing for the powering of entire computational subdisciplines. Using current DFT modelling
methods, a wide range of spectroscopic structural, optical, thermodynamic, elastic, chemical, and
vibrational properties can be estimated. Solid-state NMR and vibrational spectroscopy, which are
considered the primary tools for studying and interpreting spectra, have changed experimental
fields because of the ability to predict correlations between structure and property .The concept
of "materials by design," which holds that we can discover unique materials that outperform any
of the existing "usual suspects" for just any particular set of qualities, is a result of DFT's
amazing effectiveness in comprehending materials interactions. DFT computations can
successfully ascertain the fundamental properties and behaviour of the material under study, even
though achieving this huge goal may take some time. It is possible to determine crystal structures
that have thermodynamic stability and may be studied at ambient levels as well as under a range
of pressures by issuing a command for a specific collection of components. Calculations of
elastic constants, the density of states, band structure, and the propagation of acoustic waves can
all be made using information about the mechanical properties of crystals. DFT can also be used
to calculate the spectra of other spectral phenomena, including inelastic neutron scattering,
optical energy loss, EELS, Raman, NMR, and IR spectra. By detecting the interactions between
atoms, computing the stress tensor, and computing the lattice vector, it is possible to track the
evolution of the material structure under almost 100 picoseconds. As a result, scientists can
examine reaction kinetics and material dynamics, compute thermodynamic properties, and
establish averages. Hohenberg and Kohn introduced density functional theory in 1964. This
introduction led to the creation of the subsequent theorem. A box holding an infinite number of
electrons exposed to electronic coulomb repulsion and an external voltage v(r) displays a specific
 28

electron density n(r) functional, omitting the additive constant. The existence of the position
variable as a vector is demonstrated by the equations for density, potential, and functionals. Kohn
and Hohenberg researched the nondegenerate electron ground states and applied the reduction ad
absurdum method in their derivation. Later research, however, shown that the same theorem may
also be used to describe degraded ground states.
H=T+U+V (1)
where T is the kinetic energy operator and U denotes the electron-electron interaction, and
V = ꭍ ⱱ (r)ᴪ * c(r) ᴪ dr (2)
The functional of n(r) is defined as the sum of the T and U operators, and the charge density
functional is a universal function that is:
F[n (r) ] = ( ᴪ ( T,U ) ᴪ ) (3)
The aforementioned equation revealed that the energy functional at potential v(r) is:
Ev[n] = ꭍ ⱱ (r) n (r)dr + F[n] (4)
Hohenberg and Kohn continued by explaining that if the corrected value of ground-state density
n(r) is applied, the net number of particles is constant and the specific density functional reaches
its lowest:
N [n] = ꭍ n (r)dr = N (5)
According to Hohenberg and Kohn's first article, a system with N number of particles will have
functional energy.
E ⱱ[ᴪ ] =( ᴪ’,V ᴪ) + ( ᴪ’, (T,U) ᴪ ‘) (6)
which, when the total number of particles is constant, when compared to arbitrary alteration of
the ground state, has the lowest value at the ground state (the "corrected" ground state). The
authors showed that density n′(r), which corresponds to other potential v′(r), contributes to the
lowest value of the aforementioned energy functional, and that this value is higher than that
obtained from a system possessing ground state density n. (r). They famously came to the
inequality that follows:
ꭍ ⱱ (r) n’ (r)dr + F[n’] > ꭍ ⱱ (r) n (r)dr + F[n] (7 )
It's important to note that potential v(r) is applied to both sides of the inequality. This well-
known discovery is known as the second Hohenberg and Kohn theorem, commonly referred to as
the DFT variational principle. Additional subjects that go outside the purview of this essay were
explored by Hohenberg and Kohn. These topics range from the instance of a gas with a
 29

practically constant density to that of a gas whose density is steadily varying. Gradient
expansions were discovered in the second situation
TIME-DEPENDENT DENSITY FUNCTION THEORY
In that year, 1994, Hohenberg and Kohn made the discovery that it is sufficient to grasp the
ground-state density of a stationary electronic framework. For each of these accounts, this level
is attainable. The density is a very helpful variable since it is physically palpable, has an intuitive
understanding, and only depends upon three spatial directions, in contrast to the many body
wavefunction, which has a complex capacity of 3N spatial directions. Hohenberg and Kohn, who
also created a variational standard in terms of density, claimed that the absolute energy can be
composed as a density practical whose base, the specific ground-state energy of the framework,
is acquired at the specified thickness. So, before Thomas, Fermi, and others attempted to
synthesize their work using the total energy of a communicating electron framework as an
express expression of the density, they created a strong numerical foundation. Another change
occurred when Kohn and Sham proposed utilizing the helper noninteracting Kohn-Sham
framework to estimate the density of the cooperating framework. The Schrodinger condition for
the electrons in the Kohn-Sham framework is a simple one-molecule Schrodinger condition with
a useful outside potential. Being a consumer of electronics, as a result, the plan for this
circumstance needs to be autonomous and trustworthy. The framework's potential effectiveness,
often deteriorates
Although the second sentence includes the conventional (Hartree) aspect of electron
communication, the first phrase refers to the potential from without (typically the Coulomb
cooperation between the electrons and the cores). The complex many-body repercussions of the
(obscure) economic relations are (xc) possible. Another uncomplicated hypothesis put forth by
Kohn and Sham is the local density approximation. This method, which makes use of data on the
homogeneous electron gas's xc energy, proved to be extremely accurate for a variety of
applications and is still widely used, especially in strong state material science. The thickness
practical hypothesis (DFT), sometimes known as the density functional theory (DFT), was
developed using density as the primary variable and the Kohn-Sham framework. The original
concept was limited to an electronic framework at absolute zero with a nondegenerate ground
state, but over time, it has been expanded to cover frameworks in superconductors, relativity, and
other situations. Time-dependent density functional theory TD-DFT [45] is an expansion of
 30

distinctive nature to some extent. Runge and Gross developed a Hohenberg-Kohn-hypothesis for
the time-dependent Schrodinger condition in 1984, which lay the groundwork for the current
time-dependent density functional theory. The computation of photon absorption spectra and,
more significantly, the interaction of electromagnetic fields with the problem as the time-
dependent depiction of dispersion tests (which was Runge and Gross's initial inspiration) were all
included in the scope of this density functional theory speculation. Once more, the detailed
assumptions of Runge and Gross were based on the solid assumption that earlier work had
already verified the initial time subordinate calculations. This article looks at the advancements
made in time dependent density functional theory during the past 20 years.

HARTREE-FOCK THEORY
The virtual representation of organic macromolecules is often insufficiently detailed to
accurately reflect complicated cycles, such as the collapse of proteins, in the region where the
available potential energy capabilities exist.to improve the situation, please. It is beneficial to
leave stomach muscle initio data out of quantum mechanical computations in order to develop
less computationally taxing techniques that can be used to handle vast frameworks. In this way, it
is customary to regard the successful potential for the cores defined by the nonrelativistic
Conceived Oppenheimer estimate as a good guide to examine the accuracy of less expensive
alternatives. The study of atoms at this level of speculative detail and the design of
computationally efficient approximations for handling the requisite conditions appear to establish
the key component of the subject known as quantum mechanics. The Hartree-Fock method [47]
is used to determine the electron's energy for the static condition and approximations of the wave
equation. It is dependent on just one Slater factor
Absorption Spectra:
When electromagnetic radiation interacts with the substance, electronic changes happen.
Electronic transition [47] is the transition of an electron between two states.
According to its wavelengths and frequency, electromagnetic radiation is organized. Visible light
ranges from 400 to 800 nm, while UV is in the 10-400 nm range.
σ-σ* Transition: This shift occurs when electrons move from lower energy bonding sigma
orbitals to higher energy antibonding sigma orbitals for instance, in alkanes. These bonds are
very solid. For these transitions, very high energy is therefore required [47,48].
 31

n to σ* Transition: When one hetero atom, such as oxygen, is chemically bound to a molecule,
these transitions take place. Aldehydes, ketones, etc., require less energy than the transition from
a sigma to a sigma star, for instance. Since it takes more energy to ignite atoms with higher
electronegativity [47,48].
π-π* transition: Such transitions can be observed in unsaturated substances. Consider carbonyl
compounds. It uses less energy than the shift from a n to a sigma star.
n to π* Transition: Hetero atoms having unshared pairs of electrons shown to pi star transitions.
It needs lesser energy than other transitions in UV-VIS spectroscopy

Fig 6: Energy gap between electronic transition

 32

Results and Discussion

1. Functional Analysis:
A crucial step in theoretical investigations employing the density functional method (DFT)
and the time-dependent density functional method (TD-DFT) is the choice of an appropriate
exchange correlation functional [49]. The ground state (S0) and excited state (S1) geometries of
the studied compounds were optimized using DFT and TD-DFT with B3LYP/6-31G (d)
method. On the basis of the optimized S 1 structure, we have chosen different functionals for the
computations of delayed wavelengths (λ TADF). The λTADF value calculated at the M06/6-31G (d)
theoretical level (597.34 nm) is quite close to the experimental value (588 nm), with the
deviation being 9.34 nm. This small difference arises from the use of different density
functionals. Meanwhile, the basis set effect was also considered in this study. The λ TADF value
calculated using the 6-31G (d) basis set is similar to that of 6-31G (d,p). Therefore, the 6-31G (d)
basis set was selected in order to save computational resources. All of the calculations are
performed with the Gaussian 09 package.

Table 1. Calculated Emission wavelength (λ em) using various functionals. B3LYP/6-31g(d) is used for S 0 & S1
geometry optimization then S.P.C using different functionals and toluene as solvent via PCM model.

Functional Wavelength (nm)

6-31g(d) 6-31g(d,p)
TPSSH 915.41 909.97
HSEH1PBE 769.00 766.33
B3LYP 704.28 702.34
PBE1PBE 625.28 626.24
M06 602.09 600.44
MPW1B95 554.60 554.99
BMK 427.42 463.91
M062X 396.26 398.09
CAM-B3LYP 385.05 386.63
wB97XD 363.05 364.16
LC-wPBE 330.91 331.58
 33

Figure 3. Functional Analysis

2. Optimized structural parameters (Bond lengths and dihedral angles)

The tiny dihedral angle differences (0.1 → 4) between S0 and S1 states indicate that the
non-radiative decay from S1 to S0 is able to be suppressed effectively. For all of the designed
molecules, the largest difference between the bond lengths in the S 0 and S1 states was found
to be between the N-atom and its neighboring C-atom with a length of about 0.03 Å. The
bond lengths and dihedral angles of these derivatives change slightly between the T 1 and S1
states to within 0.02 Å and 1o respectively. It indicates that it is easy to get an efficient up-
conversion from T1 to S1 state. The distribution of the electron density plots for the T 1 states
are similar to those for the S1 states. It is also of benefit for the reverse intersystem crossing
(RISC) from the T1 to S1 states [50].

Table 2. The optimized dihedral angle (°) of the investigated systems in the S0 and S1 states using M06/6-31g(d).
 34

Dihedral Angle ɤ (°)

System/Molecule
S0 S1 S0-S1
TPA-DCPP 37.0 36.7 0.3
TPA-DCPP-tBu 34.6 38.6 4.0
PXZ-DCPP 36.99 37.2 0.3
PXZ-DCPP-tBu 36.3 36.4 0.1
CZ-DCPP 36.5 37.4 0.9
CZ-DCPP-tBu 35.95 37.4 1.5

3. Singlet-triplet energy splitting (ΔEST) and overlap between HOMOs and LUMOs.
It is well-known that the singlet-triplet energy splitting (ΔEST) should be small enough to allow
the effective ISC and RISC, leading to efficient TADF at room temperature. The ΔEST values of
compounds were obtained from the TD-DFT calculation. The ΔEST of the parent compound
TPA-DCPP is 0.1476 eV, whereas the compounds TPA-DCPP-tBu, PXZ-DCPP and PXZ-
DCPP-tBu show smaller ΔEST than that of parent compound. However, the ΔEST of compound
CZ-DCPP and CZ-DCPP-tBu is increased due to lesser electron donating ability of CZ as
compared to TPA Donor, which is harmful to the design of efficient TADF material. The change
of ΔEST values can be explained well in terms of the modification of the molecular structures.
For the compound PXZ-DCPP and PXZ-DCPP-tBu, PXZ leads to a more noticeable decrease
in ΔEST. Such small ΔEST values will induce efficient up conversion from T 1 to S1 through RISC
and increase the emission quantum yield. It can also be found that the TPA unit has much greater
influence on ΔEST values than the CZ unit. As for compounds TPA-DCPP, PXZ-DCPP-tBu
PXZ-DCPP and PXZ-DCPP-tBu although have ΔEST values smaller than that of parent
compound but -tBu derivatives further reduces the ΔEST values. Therefore, it is crucial to select
an appropriate electron-donating moiety to decrease the ΔEST for designing efficient TADF
material. We have also calculated the phosphorescence emission wavelength (λph) using the TD-
M06/6-31g(d) method on the basis of the optimized T1 states. The λph data are similar to the λTADF
data, and the small variation between the λTADF and λph values is of benefit for achieving the
TADF phenomenon [51].
 35

Table 3. Single point calculations using TD-M06/6-31g(d) Method based on optimized S 1 & T1 for the calculation of
Singlet-triplet energy splitting (ΔEST).

System name ES@S1(eV ET@T1(eV ΔEST (eV)

) )
TPA-DCPP 2.0756 1.9280 0.1476
TPA-DCPP-tBu 1.9612 1.9208 0.0404
PXZ-DCPP 1.6019 1.6014 0.0005
PXZ-DCPP-tBu 1.4506 1.4505 0.0001
CZ-DCPP 2.3770 2.0392 0.3378
CZ-DCPP-tBu 2.2169 2.0264 0.1905

4. FMO Analysis
For the sake of characterizing the optical and electronic properties, it is significant to
examine the Frontier Molecular Orbitals (HOMO and LUMO) energy levels, their energy gaps
and delocalized electron density. FMOs provide useful information about the TADF character.
The FMOs for all of these derivatives in the S 0 state show π-character and are enough to break
the electronic communication between D and A fragments. The electron density distribution of
the HOMO is located on the donor fragment, while that of LUMO is located on the acceptor
fragment and this separation decreases the exchange energy (J) which results in a smaller ΔE ST.
Hence, all of the molecules show a great separation of the HOMO and LUMO indicating that the
HOMO to LUMO transitions has a strong charge transfer character. Compared to the parent
molecules, the PXZ containing derivatives are showing a small ΔEH–L values due to its strong
electron donating strength while that of CZ containing are showing large value due to its weak
electron donating strength. We also give the density of state (DOS) analysis to support the effect
of the separation of the HOMO and LUMO Density distribution. DOS describes the number of
states per interval of energy at each energy level that are available to be occupied. A high DOS at
a specific energy level means that there are many states available for occupation. A DOS of zero
means that no states can be occupied at that energy level [52].
 36

Systems HOMO LUMO

TPA-
DCPP

TPA-
DCPP-
tBu

PXZ-
DCPP
 37

PXZ-
DCPP-
tBu

CZ-
DCPP

CZ-
DCPP-
tBu

Figure 4. HOMO-LUMO distribution of all the investigated molecules.

Table 4. HOMO-LUMO Energy Gap (ΔEL-H) using M06/6-31g(d) method based on optimize S0.

System HOMO (eV) LUMO (eV) ΔEL-H (eV)

TPA-DCPP -5.51 (200) -2.62 (201) 2.89
TPA-DCPP-tBu -5.39 (264) -2.57 (265) 2.82
PXZ-DCPP -5.21 (206) -2.94 (207) 2.27
 38

PXZ-DCPP-tBu -5.03 (270) -2.90 (271) 2.13

CZ-DCPP -5.90 (198) -2.87 (199) 3.03
CZ-DCPP-tBu -5.72 (262) -2.83 (263) 2.89

TPA-DCPP TPA-DCPP-tBu

PXZ-DCPP PXZ-DCPP-tBu
 39

CZ-DCPP CZ-DCPP-tBu
Figure 6. DPS spectrum of all the investigated molecules
5. Photophysical Properties
To gain better insight into the photophysical properties of the compounds, the UV-Visible
spectra were simulated at TD-M06/6-31G(d) level. We calculated the absorption and emission
spectra and corresponding oscillator strengths (f) in toluene solvent using PCM model.
Absorption and fluorescence intensities are generally similar if there are negligible structural
changes associated with the excitation. It is clear that the absorption wavelength increases with
donor substitution due to the increasing conjugation, resulting in a bathochromic/red shift of the
absorption maxima. Increase in the intensity of the absorption indicates that the solute is most
soluble in the solvent and that there is the lowest degree of aggregation. The oscillator strength/
intensity of the absorption (f) of TPA-DCPP-tBu is large as compared to parent compound,
indicating the increased rate of S1 → S0 radiative decay. It can be seen that the S1 transition is
from the electron-donating units to electron-accepting units for all the compounds. Taking TPA-
DCPP as a reference (597 nm), the S1 emission peaks of all the designed systems, with varying
molecular structures, are red-shifted due to increased electron donating ability of the donor. It
can also be seen that PXZ is more effective towards red-shift resulting in a larger increase in S 1
emission wavelength than CZ. Additionally, the -tBu group substitution is more effective
towards red-shift resulting in a larger increase in S 1 absorption wavelength. The similar trend is
noted for absorption spectra [53].

Table 6. Calculated λabs, λem and λPh using TD-M06/6-31g(d) Method based on optimized S0, S1 and T1 state.
System name λPh λem λabs
 40

(nm) (nm) (nm)

TPA-DCPP 643.06 597.34 523.10
TPA-DCPP-tBu 645.49 632.18 540.03
PXZ-DCPP 774.23 773.97 627.86
PXZ-DCPP-tBu 854.77 854.69 679.70
CZ-DCPP 608.01 521.61 469.40
CZ-DCPP-tBu 611.83 559.26 494.50

6. Exciton binding energy (Eb= ΔEL-H - Eflu)

The exciton binding energy is a quantity to measure the Coulomb interactions between an
electron and a hole. An exciton can be modeled as a two-particle system: one electron is
promoted into LUMO, leaving behind a hole in the HOMO. If Eb ≥ kBT (thermal energy, i.e., the
average energy of molecule at room temperature ≈ 25-27 meV), the bound excitons are stable. if
kBT ≥ Eb the bound excitons are not stable and decay into charged polaron pairs. Generally, a
large exciton binding energy is desirable in OLEDs to increase the probability of electron–hole
pair recombination. Exciton binding energy helps us to understand the attraction–repulsion
interplay between electrons and holes by comparing the variation of S 1 energy with respect to the
HOMO–LUMO energy gap. In general, excited triplet states are found to be lower compared to
the corresponding singlets; hence, we observed higher exciton binding energies for the triplets
than for their corresponding singlets. Exciton binding energies were found to be higher in the
solvent phase than in the gas phase. Although, the designed molecules have smaller Eb than the
parent molecule but still Eb ≥ kBT [54].

Table 7. Calculated Exciton binding energy (Eb)

Exciton binding energy

System name ΔEL-H (eV) Eflu (eV)
Eb = ΔEL-H - Eflu
TPA-DCPP 2.89 2.08 0.81
TPA-DCPP-tBu 2.82 1.96 0.86
 41

PXZ-DCPP 2.27 1.60 0.67

PXZ-DCPP-tBu 2.13 1.45 0.68
CZ-DCPP 3.03 2.38 0.65
CZ-DCPP-tBu 2.89 2.22 0.67

7. Charge injection and transport Analysis

The charge injection and transport abilities of the optoelectronic compounds are
important for their device performance. Generally, the ionization potential (IP v, IPa), electronic
affinity (EAv, EAa), hole extraction potential (HEP) and electron extraction potential (EEP), hole
reorganization energies (λh), electron reorganization energies (λe) are used to study the charge
injection ability of the materials. Generally, if the IPv is lower and the EAv is higher, the injection
of holes and electrons from hole and electron transport layer/host material to emitter is easier.
The IPv values of PXZ derivative is lower than that of parent compound, suggesting a better
hole injection. Thus, increasing electron donating ability of the donor was deemed to be an
effective way to improve the hole injection ability of material. However, the IP v values of -Cz
containing derivative is larger than that of parent compound, indicating that the carbazole group
has an inverse influence on the improvement of hole injection capacity. The EA v of both, the
PXZ as well as CZ containing derivatives is larger than the parent compound demonstrating that
the electron injections from electron transport layer/host material to emitter is much easier.
Reorganization energy (λ) quantifies the energetic response of a molecule due to its
geometric rearrangement upon charging or discharging. According to the Marcus theory, a low
reorganization energy value is required for an efficient charge transfer rate and balance between
the hole and electron reorganization energy (λh and λe) for the efficient TADF compounds.
It can be seen that λ h of both , the PXZ as well as CZ containing derivatives, are higher than
that of parent compound and are in a range of 0.067 eV to 0.141 eV but are smaller than that of
the typical hole transport material (0.29 eV).
The λe values of both, the PXZ as well as CZ containing derivatives, are smaller than that of
parent compound and are in the range of 0.013eV to 0.079eV which are also smaller than that of
the classical electron transport material (0.28 eV) N, N0-diphenylN, N-bis(3-methyl-phenyl) -
(1,10-biphenyl)-4,40-diamine (TPD, 0.29 eV), tri(8-hydroxyquinolinato) aluminum(III).
 42

Thus, we estimated the λh/e values for all compounds by potential energy surface method. Such
large difference between λh/e is discussed through the analysis of molecular structures between
ionic and neutral states. It is worthwhile that these bond lengths and dihedral angles at neutral
state are very similar to those at cationic state. However, these bond lengths and dihedral angles
at anionic state are far away from those at neutral/cationic states. Therefore, the large structural
variation at anionic states leads to great λh. (Χ = (IPv + EAv)/2 corresponds to Electronegativity)
[55].

Table 9. DFT estimates of vertical and adiabatic ionization potentials (IP v and IPa), electronic affinities (EAv and
EAa), hole and electron extraction potentials (HEP and EEP), and reorganization energies (λh and λe) in eV).

System Name IPv IPa HEP EAv EAa EEP λe λh Χ

0.06
TPA-DCPP 6.292 6.258 6.225 1.557 1.512 -1.636 0.079 3.92
7
0.07
TPA-DCPP-tBu 6.123 6.144 6.045 1.526 1.461 -0.005 -1.521 3.82
8
0.14
PXZ-DCPP 6.076 5.986 5.936 1.849 1.772 -1.862 0.013 3.96
1
0.07
PXZ-DCPP-tBu 5.808 5.779 5.734 1.820 1.943 -2.066 0.246 3.81
5
0.07
CZ-DCPP 6.702 6.667 6.626 1.786 1.696 -1.812 0.025 4.24
6
0.05
CZ-DCPP-tBu 6.453 6.423 6.394 1.759 1.677 -1.776 0.017 4.11
9
 43

CONCLUSION:
In summary, we have designed a series of TPA-DCPP-based TADF emitters with different
donor fragments. Our calculations revealed that the PXZ containing compounds have smaller
while CZ containing compounds have larger ΔEST values than the parent compound. For the
same topological compounds, the ΔEST values decrease with increasing electron donating-
strength of donor moieties. Then, a systematic theoretical investigation of the charge injection
and transport analysis for the designed compounds was performed using M06/6-31G* method.
The IPv values of PXZ derivative are lower than that of parent compound, suggesting a better
hole injection. Thus, increasing electron donating ability of the donor was deemed to be an
effective way to improve the hole injection ability of material. However, the IP v values of Cz
containing derivative is larger than that of parent compound, indicating that the carbazole group
has an inverse influence on the improvement of hole injection capacity. The EA v of both, the
PXZ as well as CZ containing derivatives is larger than the parent compound demonstrating that
the electron injections from electron transport layer/host material to emitter is much easier.

The designed compound CZ-DCPP exhibit more effective charge injection with lower IP and
higher EA values than those of the parent compound TPA-DCPP. The binding energy values of
all the designed molecules DMAZ-DCPP, PXZ-DCPP, and CZ-DCPP are lower than that of
parent molecule TPA-DCPP. The emission and absorption wavelengths of DMAC-DCPP and
PXZ-DCPP are larger while CZ-DCPP has a smaller value than TPA-DCPP. Meanwhile, the
newly designed compounds DMAC-DCPP and PXZ-DCPP possess higher carrier mobility than
parent TPA-DCPP. Therefore, the designed DMAC-DCPP and PXZ-DCPP compounds may
be better carrier transport materials with higher mobility for TADF-based OLEDs. Among all the
investigated materials DMAC-DCPP and PXZ-DCPP with a lower value of ΔEST (0.0001,
0.0005 eV) and emission wavelength in the region of (651 and 774 nm) are considered the best
candidate for red to NIR-TADF materials. We believe that our theoretical calculation will help in
understanding and designing higher-performance TADF-based OLEDs.
 44

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