available online @ www.pccc.icrc.ac.

ir
Progress in Color Colorants Coating 17 (2024), 417-433

A Review of the Application of Organic Dyes Based on Naphthalimide in Optical

and Electrical Devices
M. Hosseinnezhad1, 2*, S. Nasiri3, V. Nutalapati4, K. Gharanjig1, A. M. Arabi5
1.
Department of Organic Colorants, Institute for Color Science and Technology, P.O. Box 16765-654, Tehran, Iran.
2.
International Scientific Studies and Cooperation Center of the Ministry of Science, Research and Technology, P.O.
Box: 33535111, Tehran, Iran.
3.
Faculty of Mechanical Engineering and Design, Kaunas University of Technology, Studentu Street 56, Kaunas, LT
51373, Lithuania
4.
Functional Materials Laboratory, Department of Chemistry, Faculty of Engineering and Technology, SRM Institute of
Science and Technology, SRM Nagar, Kattankulathur 603203, India
5.
Department of Inorganic Pigments and Glaze, Institute for Color Science and Technology, P.O. Box: 16765-654,
Tehran, Iran

ARTICLE INFO

Article history:
he two technologies of dye-sensitized solar cells (DSSCs) and organic
Received: 20 Nov 2023
Final Revised: 02 Feb 2024
Accepted: 03 Feb 2024
T light-emitting devices (OLEDs) are emerging in the development of new
sources of energy and lighting, respectively. The exceptional features of
these technologies, including their color, insensitivity to temperature, and high
Available online: 29 May 2024
response angle, have caused their attention and development. Organic
Keywords: compounds play a key role in these two technologies and cause the effective
Dye-sensitized solar cells response and stability of the device, so high stability, longevity, and the
Organic light-emitting devices possibility of simple application in the structure of the structure are of great
Napthalimides importance. Molecular engineering and the application of various substitutions
Photovoltaic to the naphthalimide core can produce promising results for the preparation of
Luminescence stable organic materials with diversity in properties. In this review,
naphthalimides are introduced as an effective core in the preparation of light-
and electricity-sensitive dyes. Its application in two technologies, DSSCs and
OLED, is explained, and the different components of these technologies are
briefly introduced. One of the highest efficiencies reported for dye-sensitized
solar cells based on naphthalimide as photosensitizers is 10.8 %. This sensitizer
has alkyl and indoline groups. Different structures of arrangement of electron
donor and electron acceptor groups will be investigated and the performance
efficiency of these devices will also be investigated. Studies show that the amino
group is an important substitution in the preparation of naphthalamide
fluorescent dyes. The presence of this group will increase the efficiency of the
amplifier by up to 10 %. Prog. Color Colorants Coat. 17 (2024), 417-433©
Institute for Color Science and Technology.

1. Introduction the importance of providing new sources and forms of

The issues of energy and economy are very important in energy are very important for the development of
human life because these two factors improve the social technology. The development of energy resources
welfare index. The growth of energy consumption and should be done in such a way that, in addition to the ease

*Corresponding author: * hosseinnezhad-mo@icrc.ac.ir

https://doi.org/ 10.30509/pccc.2024.167247.1267
 M. Hosseinnezhad et al.

of procurement, it avoids environmental pollution and preparing silicon modules and expanding its use in
does not reduce air quality. In other words, in order to spacecraft was investigated. The sudden need for this
preserve the human race, the introduction of broad, safe technology was announced with the possibility of
and environmentally friendly energy sources should be diminishing fossil fuel resources and oil embargoes in
considered. All countries should invest in this issue 1976. Until now, the commercial market for
because the development of clean energy has a direct photovoltaics has been dominated by silicon-based solar
impact on life expectancy [1]. The epidemic of Corona cells due to their high efficiency, good stability, and low
disease showed that health and related research are very energy loss. But this technology also has weaknesses,
important. In addition, during this period, energy such as: dependence on temperature, lack of response in
consumption increased significantly, but due to the mild and cloudy conditions, high weight of modules, and
limitations of industrial activity, fossil energy the fragile nature of the device [5]. In 1960, anthracene
consumption decreased. Therefore, renewable energy was introduced as an organic compound with optical
sources and the energy produced by them were conductivity, and later, with the expansion of research,
considered and consumed. Research shows that energy compounds with conjugated systems that have electrical
production, economic growth, and life expectancy have conductivity were also discovered. Research has shown
linear and non-linear effects on each other. Factors such that increasing the conjugation system helps to improve
as the cost of living, technological development, conductivity. Therefore, the second generation of solar
increasing the heat of the earth, and the production of cells was prepared as thin-film devices. Due to its high
carbon dioxide gas are caused by these factors [2]. Of cost and complex production methods, this technology
course, the life expectancy index varies according to did not receive public attention and could not develop
countries' incomes, and countries with high incomes significantly. Therefore, many efforts were made to
have a lower life expectancy than countries with lower develop new photosensitive materials and, to study
incomes [3]. Electrical energy has increased layering methods and intramolecular and interlayer
dramatically due to the increase in electrical tools used, interactions [6]. Figure 1 shows the publication process
and alternative ways to reduce energy consumption and of articles in the photovoltaic field [7]. As a result of this
replace them with light-emitting devices with high research, electroluminescence conjugated polymers,
efficiency should be considered. Another common diodes, transistors, and organic photovoltaic devices
method for classifying dyes is the method of their use or were introduced. One of the most important technologies
functional classification. Dyes have a variety of developed in 1991 by Gratzel and his colleagues was
applications in various industries, including: dyeing solar cells sensitized to dyes [8]. In the following, this
textiles, food and health products, medicine, coloring technology will be introduced.
polymers, optics, lasers, photonics, etc. The production
of energy and light is one of the emerging applications
of dyes, which is very important for the development
and progress of humans' lives [3]. In this article, two
types of energy, including photovoltaic and electric
energy, are investigated. The device of each case is
introduced, and the role of dyes, especially
naphthalimide dyes, is studied.

2. Photovoltaic devices
The photovoltaic effect was discovered in 1839 by
Edmond Becquerel. After that, with the development of
research, photoactive and photoelectric effects were
introduced. The response of silicon to light was Figure 1: Published articles in the field of photovoltaics
accidentally discovered in 1953 and led to the [7] (Reprinted with permission from [7]. Copyright 2023,
production of the first generation of photovoltaic Elsevier Publishing due to open access).

devices. Then, the development of this technology by

418 Prog. Color Colorants Coat. 17 (2024), 417-433

A Review of the Application of Organic Dyes Based on Naphthalimide in Optical and …

2.1. Dye-sensitized solar cells of the solar cell is due to leakage of the electrolyte or
Renewable energy sources are important for energy its evaporation. When the electrolyte is not able to
production, and one of the most important of them is supply the lost electron of the sensitizer, the return to
solar energy, which is abundant and easily available in the base state is not transferred, and the sensitizer,
many countries. Among the devices produced for the which is the main part of the electron production, is
use of solar energy, dye-sensitized solar cells (DSSCs) destroyed. DSSCs efficiency is calculated based on
are very desirable because of their low cost, colorful, photocurrent (Jsc), photovoltage (Voc), and fill factor
and the possibility of being used in building design, (FF) parameters (Eq. 1) [9].
ease of preparation, and insensitivity to temperature
and light changes [9, 10]. As shown in Figure 1, this (1)
device (DSSCs) has several essential and important
parts. Two electrodes, anode and cathode, are Each of these factors can be increased by
necessary to complete the electrical circuit. To prepare optimizing the components of the DSSCs, and as a
the anode electrode, a semiconductor layer is placed on result, the efficiency of the device increases. For
a conductive substrate, the indicated layer, and then the example, using a suitable photosensitizer that can have
sensitizer is placed on it. The cathode electrode, or a high response to light and establish a stronger
counter electrode, is prepared from the address layer of connection with the semiconductor pores will increase
a platinum layer on the conductor substrate. The the photocurrent. To prepare a suitable device, it is
presence of a redox couple as an electrolyte is important to obtain high efficiency and low cost, and
necessary to supply the excited transition electron of a this is achieved by engineering and designing different
semiconductor. In this technology, an electric current is parts of this technology. Engineering energy levels
produced by stimulating the sensitizer (dye) against of the electrolyte, photosensitizer, and semiconductor
sunlight. By receiving sunlight, the sensitizer transfers conduction band lead to an increase in photocurrent.
its valence layer electron to the lowest empty molecular Calculations show that the amount of photocurrent
orbital. In a thermodynamic process, the excited can be increased up to 1.6 volts. Shunt and serial
electron is transferred to the conduction band of the resistance are two important factors in determining
semiconductor and enters the electric circuit. Next, the the filling factor, which is caused by the function
electrolyte supplies the lack of sensitizing electrons of electron transfer in the electrodes. As mentioned,
needed to create the ground state and prevent its the photosensitizer has a main and important role in
destruction. This cycle continues until all the the structure of the DSSCs, which will be discussed
components do their jobs. Usually, the end of the life further [9].

Figure 2: Schematic and working digram of DSSCs.

Prog. Color Colorants Coat. 17 (2024), 417-433 419

 M. Hosseinnezhad et al.

2.2. Photosensitizers is the possibility of aggregation on the semiconductor

The photosensitizer (dye) in the structure of the DSSCs surface and the lack of production and transfer of
plays the role of producing electrons. In other words, excited electrons [15]. In order to prepare a suitable
these components absorb sunlight and convert it into photosensitizer that has minimal aggregation,
electrical energy. In order for a chemical compound to chromophores and a skeleton that have high
be used as a sensitizer in the structure of a solar cell, it photophysical and electrochemical characteristics
must have a number of characteristics, which include: a should be used in addition to the proper configuration.
wide absorption range in the visible and near-infrared In the design of light-sensitive molecules, the electron-
region, the ability to create effective bonds with donating and electron-accepting groups are connected
semiconductors, a LUMO energy range lower than the to each other with a conjugated system, which is also
semiconductor conduction band, the ability to receive the main point of connection to the semiconductor
electrons from the redox couple and high fating. Dyes surface. For each of these parts, a variety of groups and
used in the structure of DSSCs are divided into three chemical structures can be used, and this choice is
categories: organometallic, organic metal-free, and better to expand the conjugated system [16, 17].
natural. In this classification, organometallic dyes have 1,8-Naphthalimides are one of the most effective
the highest efficiency and technical characteristics, but chemical structures and skeletons in the preparation of
the preparation process is complicated, expensive, and all kinds of light-sensitive and fluorescent dyes. The
polluting. Organic dyes have a simpler process and most important feature of this class is their high
high reproducibility, but on the other hand, their thermal stability, high electron affinity, and oxidation
efficiency is lower than organometallics. Natural dyes stability, which has led to the development and
can be obtained from various sources, such as seeds, expansion of this type of compound. Naphthalimides
flowers, leaves, fruits, stems, etc., and do not pollute (Figure 3) dissolve better in water than diimine and
the environment. These materials are very cheap, and pyridine derivatives, making them a more interesting
widely available, and have a very simple preparation research topic [18]. In these structures, the naphthalene
process. The most important drawback of this class is ring acts as a conjugate bridge that connects electron-
their very low yield. One of the important technologies donating and electron-accepting groups. Organic
to improve the final efficiency of the sensitizer in the compounds based on naphthalimide have high thermal
solar cell is the use of quantum dots. As mentioned, stability and often have good fluorescence emission
organic dyes are in the middle in efficiency and ease of power. Engineering the chemical groups at the 4-
preparation. Many researchers have looked into this position of the naphthalimide ring can change the
issue, and structural engineering is crucial for the fluorescence intensity. The effectiveness of position 4
efficient preparation of metal-free compounds [11, 12]. has also been confirmed in theoretical calculations.
In many new technologies, such as optical compounds, Therefore, naphthalimide-based structures have wide
sensors, and drugs, the use of naphthalimides and applications in molecular imaging, analytical
their derivatives has been suggested. Because chemistry, material chemistry, and medicine [19, 20].
naphthalimides have a cost-effective synthesis process In the following, an overview of the applications of
and their optical properties can be engineered [13]. In naphthalimides as sensitizers in the DSSCs structure
the following, the use of naphthalimide in the will be presented.
preparation of highly efficient sensitizers is described. Lin et al. prepared a naphthalimide structure
containing an alkyl carboxyl chain for use in DSSCs. A
carboxylic acid group was chosen to create an effective
2.2.1. Photosensitizers based on naphthalimide
bond on the semiconductor, and finally, the prepared
Metal-free organic compounds are one of the suitable
dye has a medium emission in the green area. The
options for use in DSSCs, which have many
prepared dye showed 10.8 % efficiency in the DSSCs,
advantages. The strengths of these compounds are:
while the efficiency doubled when combined with
high molar absorption coefficient, diversity in
N719 [21]. Since indolines are great for making
molecular structure design, many chemical structures,
sensitizers, adding naphthalimides as an electron-
ease of preparation, high reproducibility, etc. [14]. One
accepting group should make this structure work better.
of the most important weaknesses of these compounds

420 Prog. Color Colorants Coat. 17 (2024), 417-433

A Review of the Application of Organic Dyes Based on Naphthalimide in Optical and …

R
O O
O N O

N N
N N
O O

R
Naphthalene diimide
1,8-Naphthalimide

O O

H N N H

O O

Perylene bisimide
Figure 3: Naphthalimide and its derivatives [18, 19].

Saini et al. designed this approach for the and using acenaphthene as the starting material. The
preparation of light-sensitive dyes with D-A-π-A maximum absorption of the prepared dyes was
arrangements. Scientists looked at cyanoacrylic acid observed in the region of 427-435 nm and it was
mixed with naphthalimide, which acts as an electron deposited on two types of semiconductors. The shift in
acceptor. They found that the color performance got the absorption peak revealed a slight aggregation of
better as the distance between these two groups got synthetic dyes on the semiconductors. The efficiency
bigger. In addition, the elevation of the conjugated obtained for dyes in the DSSCs is about 1.3 % [25].
system causes the absorption maximum to shift to Some researchers have used computational methods
higher wavelengths and create a red hue. The highest to extract the optimal structure of organic dyes based
efficiency reported in this series of compounds is on naphthalimide. In research, eight T-shaped organic
around 5 % [22]. Three organic azo dyes were prepared dyes that had a naphthalimide conjugate bridge were
using the naphthalimide group for use in DSSCs. In investigated with DFT. Some important factors in the
this research, the effect of different electron acceptor DSSCs, such as efficiency, light harvesting rate,
groups and their distance to the naphthalimide group electron injection current, and the return cycle of the
was investigated and evaluated. The results showed dye to the base state, were considered effective factors
that all the prepared dyes have aggregation on the in the calculations. The findings showed that the
semiconductor, and to prepare the DSSCs, it is naphthalimide structure creates a structure that stops
necessary to use an anti-aggregation agent. The highest aggregation and energy levels that are good for solar
efficiency in the DSSCs was obtained for the dye cells [26]. It was looked into what happens when
with cyanoacrylic acid and four double bonds naphthalimide is added as an acceptor electron group to
with the naphthalimide group, or about 4.82 % [23]. phenothiazine-based organic dyes. In these compounds,
Nucleophilic and Suzuki coupling reactions were used naphthalimide is placed at the 7-position of the
to connect the pyrazinyl group to the nitrogen of the phenothiazine ring by a triple bond. The efficiency of
naphthalimide ring, and two organic dyes with intense the DSSCs prepared using these dyes was reported at
green fluorescence were prepared. The synthesized 4.9 % [27]. Recently, studies have been published on
dyes have a melting point of 300 ºC and a monoclinic the preparation of organometallic complexes using
crystal structure. Synthesized dyes have many naphthalimide units for use in DSSCs. In particular, a
intermolecular interactions that cause accumulation heteroleptic complex was made with naphthalimide
potential in the layers. On the other hand, it has high and phenanthroline as its building blocks and copper as
optical and thermal stability, which makes it suitable its main metal. Studies showed that the presence of
for use in light-sensitive structures [24]. Three organic these chemical structures causes a 32 % increase in
dyes (Figure 4) were prepared based on naphthalimide quantum efficiency and a 20 % in DSSCs conversion

Prog. Color Colorants Coat. 17 (2024), 417-433 421

 M. Hosseinnezhad et al.

Figure 4: Chemical structure of dyes based on napnthalimide and their performance [25].

efficiency, and this performance improvement is due to production of lighting has been considered. For
the presence of naphthalimide groups [28]. In another example, the efficiency of ordinary lamps is 16 IM/W,
study, a 4-ethynyl-naphthalimide group was selected to fluorescent lamps are 70 IM/W, and LED lamps are
prepare an organometallic complex with cobalt as the 300 IM/W. As a result, LED technology replaced older
central metal. The results showed that, due to the energy sources. A more recent approach is to use a
increase in the length of the conjugated system, light-emitting organic compound (without or with
absorption and emission are transferred to higher doping), which is known as OLED (organic light-
wavelengths. The prepared complex has a thriclinic emitting diodes) [30]. Recently, the issue of OLED has
crystal structure and has two oxidation maxima in received attention in industry and academia due to the
voltammetry behavior. As a result, the prepared widespread use of this technology in smartphone
structure can be used as a sensitizer in the solar cell screens, TV screens, and lighting production panels.
structure [29]. This technology has many advantages over liquid
crystal displays and has been significantly developed in
3. OLED devices the display industry. The advantages of this technology
include: no need for background light; low thickness
Providing sources of energy and lighting production is
and weight; high contrast; high response time; high
important because of their widespread use in life,
resolution; and the possibility of preparing flexible
especially in business and advertising. Therefore, the
samples [31]. OLED is prepared in multi-layers, and
introduction of low cost and efficient methods for the

422 Prog. Color Colorants Coat. 17 (2024), 417-433

A Review of the Application of Organic Dyes Based on Naphthalimide in Optical and …

these layers are placed on top of each other decay from S1 to S0 (ground state) causes fluorescence
successively with different methods. Conventional at a high rate compared to forbidden processes
methods for this purpose are: plasma with evaporation, (intersystem crossings). Therefore, the use of
spin coating, and thermal evaporation with vacuum. fluorescent compounds in OLED causes the non-
The simplest device is made of three layers, including radiative decay of all triplet excitons and the quantum
the radiating layer and two electrodes. This device has efficiency is limited to a maximum of 25 % (Figure 6)
low efficiency due to the large hole-electron gap. This [30, 31].
problem can be solved by using a multi-layered system The preparation of new compounds with the
with organic materials with charge transfer properties. possibility of phosphorylating is the subject of much
These compounds are used as electron-hole regions research in the field of materials used in OLED. For
(Figure 5) [30]. this purpose, increasing the spin-orbit coupling (SOC)
Applying an external voltage between two is used. Theoretically, such devices are able to provide
electrodes produces holes in the anode and electrons in 100% efficiency. Organometallic complexes have such
the cathode. Holes move towards the highest occupied properties, and compounds based on Ir (III) and Pt (II)
molecular orbital (HOMO), and electrons move are known as the most efficient green and red emitters.
towards the lowest unoccupied molecular orbital But blue emitters can hardly be produced by this
(LUMO). Electrons and holes produced in the method, and for this purpose, the first-generation
recombination region come close to each other, and method with low efficiency must be used [30]. A lot of
due to Coulomb interactions, excitons are produced. research is being done to improve the performance and
According to exciton statistics, electrons and holes can efficiency of fluorescent devices in industry and
form four different exciton states, one singlet and three universities. Areas such as the preparation of blue and
triplets, in a ratio of 1:3. According to the orbital red luminescent materials need more attention and
conservation law, the spins remain unchanged until the research. Research published in this field in the years
molecularly excited levels are filled. Singlet and triplet 2000-2020 is shown in Figure 7, which shows that the
excitons fill the singlet and triplet molecular levels, progress of water technology requires unique materials
respectively. According to statistics, 75 % of molecules and products [31].
are in the T1 state and 25% in the S1 state. The rapid

Figure 5: OLED configuration [30] Left: monolayer configuration, and right: multi-layer configuration (reprinted with
permission from [30]. Copyright 2020; Elsevier publishing due to open access).

Prog. Color Colorants Coat. 17 (2024), 417-433 423

 M. Hosseinnezhad et al.

Figure 6: Emission mechanism in OLEDs [30]; (Reprinted with permission from [30]. Copyright 2020; Elsevier publishing
due to open access).

Figure 7: The number of articles and patents published in the field of water [31]; (reprinted with permission from [31].
Copyright 2021; Wiley Publishing due to open access).

3.1. Emitters for application in OLEDs toluene, chlorobenzene, and tetrahydrofuran (THF). To
Much research has been done to prepare highly efficient get around interactions within and between molecules,
phosphors to be used as emitters in OLED devices. One twisted and non-planar structures are often suggested to
approach to classifing these compounds is based on their make sure high phosphorescence efficiency. In some
chemical structure, which includes: small molecules, cases, the low solubility of these compounds limits the
dendritic, and polymeric phosphorescent emitter.Small performance of electroluminescence. On the other hand,
molecule phosphors are proposed as dopant emitters due heterogeneous morphology causes phase separation
to their good solubility in processing solvents such as between the host matrix and the radiating component. To

424 Prog. Color Colorants Coat. 17 (2024), 417-433

A Review of the Application of Organic Dyes Based on Naphthalimide in Optical and …

overcome the dissolution limitation, it is possible to complex unit, an unconjugated system with a repeating
substitute aliphatic chains in molecules. One way to complex unit, and an organic polymer attached to a
make it easier to dissolve is to add an alkoxy group to metal complex. A vinyl-type polynorbornene
the para-nitrogen position of the difluorophenylpyridine copolymer containing iridium and biphenyl complexes
group. Many small-molecule complexes with Ir, Au, and as side groups was prepared, which had a red emission
Pt as central metals have been developed for with a yield of 5.1%. A similar structure was prepared
fluorescence in the green-red region. In addition, in the presence of conjugated polycarbazole, which
iridium-based complexes have the ability to provide showed intense green emission with a yield of 9.6 %
orange phosphorescence, but their electroluminescence [34]. The advantages of polymer light-emitting
efficiency is relatively low. The prepared complexes, materials are: low production cost, homogeneous
with platinum central metal and carbazole ligands or emission, no phase separation, and very high spectral
functionalized acetylides, show red fluorescence in the stability. Studies show that molecular design has a
green region with high intensity. Recently, the effect of direct effect on emission efficiency, and thermal and
CN groups on the fluorescence of platinum complexes photophysical properties. Issues that are effective in the
was evaluated, and the results showed that these design and synthesis of light-emitting polymers are:
compounds have high fluorescence efficiency in the appropriate host compositions, an appropriate energy
yellow and green regions [32]. gap between the HOMO and LUMO layers; and charge
There are metal complexes with dendritic networks current balance.
that are often used as dendritic phosphorescence In luminescent polymers, it is important to control
materials. By changing the dendron metal, these the interactions between and within molecules so that
materials can improve the light emission. Biphenyl steric effects don't cause interactions that stop the
dendrons on the iridium metal core, which have an emission. Studies show that iridium has the best
anchoring position, have a high fluorescence efficiency. performance in the preparation of light-emitting
The prepared film with these compounds has a higher polymers, and its emission efficiency is higher
efficiency than the fluorescence compound solution. compared to other central metals with the same
Triphenylaminedendrons with iridium as the central structure [35].
metal have a red emission and a quantum efficiency of
11.7 %. The use of triarylamines can increase the 3.2. Naphthalimide in OLEDs
intensity of fluorescence. A class of fluorescent Naphthalimides have a planar conjugated system that
dendrimers was prepared using iridium and conjugated has unique optical, electrochemical, and photoelectric
carbazoles to provide green fluorescence with an properties. Naphthalimides are very suitable for
efficiency of about 10 %. In addition to the preparation preparing light-emitting compounds, which are used in
of new fluorescent materials, the way they are used also light-emitting sensors, ion probes, and optical and
affects their performance and final yield. For example, electrical devices. Naphthalimide-based organic
encapsulation of dendritic materials (especially in the molecules have an electron-deficient nucleus that has
presence of iridium metal) it reduces the possibility of carbonyl groups. This arrangement can cause a low
fluorescence quenching due to unwanted aggregations, reduction potential and a high energy gap, so it is
and on the other hand, it increases the ease of making excellent for preparing N-type organic semiconductors.
successive layers in the presence of various solvents. On These compounds are very efficient illuminants that
the other hand, these compounds are able to provide have very good efficiency. This good performance is
fluorescence with a specific color, which is obtained due to the high chemical and optical stability, the
through the combination of several dendritic possibility of setting the value of the emission range,
fluorescence materials with different emissions. In and the ability to form a film. The electronic properties
addition, by carefully adjusting the dendron, unwanted of naphthalimide-based luminescent materials have a
impurities can be eliminated [32, 33]. direct effect on the color emitted in OLED devices. The
Some polymers that have an organometallic nature and placement of substituents on the
complex have been prepared as emitters. There are naphthalimide core have a direct effect on chemical
different arrangements for preparing these compounds, and physical behaviors and sensitivity to light and
including: a conjugated system with a repeating electricity. All kinds of amines are suggested for the

Prog. Color Colorants Coat. 17 (2024), 417-433 425

 M. Hosseinnezhad et al.

reaction and preparation of emitternaphthalimide The naphthalimide ring was made brighter by
derivatives. These groups can be placed on the nitrogen adding carbazole to positions 2 and 9 of the
ring or in the free positions of the aromatic ring. naphthalimide ring (through a click reaction) and then
Another effective strategy is to increase the conjugated polymerizing it. The results showed that the oxidation
system. The positions 3 and 4 of the naphthalimide ring and reaction of the substituted compound in position 2
are very suitable for replacing halogen, nitro, and are easier than in position 9. This difference is due to
amino groups. The addition of amino and alkoxy the participation of oxygen and nitrogen electrons in
substituents as electron-donating groups in positions 3, the conjugated structure in substitution at position 2
4, 5 or 6 of the aromatic ring can improve the emission [37]. An organic dye was synthesized based on
efficiency due to the creation of an excited surface of naphthalimide with a D-π-A configuration. CV studies
polar charge. Placing the right substituents in good showed that the transfer process involves a single
places can control and engineer the emission range electron. The effect of the solvent on the synthesized
from blue to green or yellow. The emission range will compounds was investigated, and the results showed
be red-shifted if aromatic groups are attached to the that with an increase in the polarity of the solvent, the
nitrogen of the naphthalimide unit. The electron red hue created is due to the stabilization of the more
mobility and affinity of naphthalimide derivatives are polar state in the presence of polar solvents. These
about 3.1 and 0.16 eV, respectively. This makes them compounds have intramolecular rotations and show
perfect for making stable materials that give off a lot of stronger diffusion in polar solvents or their mixtures. If
light. The image of naphthalimides with different you add an extra phenyl group to the chromophore, it
illumination is shown in Figure 8 [36]. In the has better optical properties because it makes the
following, an overview of the applications of electron flow process easier [38]. We made 12 kinds of
naphthalimides as sensitizers in the OLED structure light-emitting molecules (Figure 9) by putting phenoxy
will be presented. groups with aldehyde and nitrile in the fourth position
of the naphthalimide ring. These dyes were prepared
from acenaphthene as a raw material using reactions
such as bromination, imidation, and oxidation. These
compounds are stable up to 260–280 ºC and have a
band gap in the 2.83-3.02 eV range with deep blue
fluorescence. The highest quantum efficiency reported
for these materials is about 1.4 % [36].
In a new approach, benzo and naphthodioxane are
fused together and added to the naphthalimide
structure. For the preparation of these compounds, the
most important reaction is bromination, which places
three different bromines in the naphthalimide core. The
prepared dyes were stable up to 400 degrees and
showed a green emission in the OLED structure and a
yield of 6.9% [39]. In another study, the effect of the
presence of imine and beta-ketoanamine units at the 3-
position of the naphthalimide nucleus was investigated.
The effect of substitution group, bond type, and
substitution site in naphthalene ring on thermal,
electrochemical, optical and electrical properties was
investigated. The results showed that imines are more
prone to hydrolysis and ketoanamine has unwanted
accumulations in the excited state. Therefore, based on
Figure 8: Schematic illustration of naphthalimides as
emitter in OLED [36]; (Reprinted with permission from the conditions and the final application, the type of
[36]. Copyright 2022; Springer Publishing due to open substitution chosen is different [40, 41]. A chiral
access). molecule based on naphthalimide with red emission

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and high thermal stability (405 ºC) was prepared. The conjugated system grew, which caused the emission
synthesized compounds have a strong red emission in wavelength to shift by a bathochromic amount. These
the region of 592 nm, and a quantum efficiency of compounds did not show quenching effects with red
12.4 % and show high electrochemical properties [42]. emission at any concentration. Studies showed that the
The presence of an imine substituent in the conjugated use of the CN group increased the life of fluorescence.
system, which connects the phenyl group to the Naphthalimides have different hues, from white to
naphthalimide body, provides a wide range of emitting water (Table 1). Molecular engineering and the
hues. Gan et al. prepared two series of naphthalimides placement of suitable substitutions are two methods for
with hydrazone substituents (Figure 10). By adding achieving this diversity [36].
different amino acids to these compounds, the

Figure 9: Fluorescence chromophores based on naphthalimide with blue emission [36]; (Reprinted with permission from
[36]. Copyright 2022; Springer Publishing due to open access).

Figure 10: Naphthalimide compounds with red emission [36]; (Reprinted with permission from [36]. Copyright 2022;
Springer Publishing due to open access).

Prog. Color Colorants Coat. 17 (2024), 417-433 427

 M. Hosseinnezhad et al.

Table 1: Luminescent naphthalimides for use in OLED structure [36]; (Reprinted with permission from [36]. Copyright
2022; Springer Publishing due to open access).
λemission Turn-on Volt ηEQE
Molecular Structure
(nm) (V) (%)
Blue emitters
O Br

N 482 3 3.2

O Br
Br

O
487 7.7 0.42
O
N
OH
O
Cl

O
516 8.25 0.28
O
N
OH
O
Cl

O
O 516 6.92 0.47
N O
O
O CH3

Green emitters

O
N 530 5.8 1.11
N

O
N O

S N 556 10 0.2

428 Prog. Color Colorants Coat. 17 (2024), 417-433

A Review of the Application of Organic Dyes Based on Naphthalimide in Optical and …

Table 1: Continue.
λemission Turn-on Volt ηEQE
Molecular Structure
(nm) (V) (%)
Blue emitters
N O

N N 544 7 0.22

H 3C O
N 530 6 0.26
H 3C N

O
Orange emitters

O
N
562 - 0.91
N

H3C O
N CH3 597 3 4.59
H 3C N CH 3
CH3
O

S
H 3C O 641 4 9.2
N CH 3
H 3C N CH 3
CH 3
O

Prog. Color Colorants Coat. 17 (2024), 417-433 429

 M. Hosseinnezhad et al.

Table 1: Continue.
λemission Turn-on Volt ηEQE
Molecular Structure
(nm) (V) (%)
Blue emitters

O
H 3C O 590 3 20.3
N CH 3
H 3C N CH 3
CH 3
O

Red emitters
N(CH3)2

N O 620 14 3.59
N
H
N nBu

O
657 3.7 7.0
N

O CH 3 N

N
576 3.5 1.8
N

O
H 3C
CH 3

583 2.9 7.59

N CH 3

430 Prog. Color Colorants Coat. 17 (2024), 417-433

A Review of the Application of Organic Dyes Based on Naphthalimide in Optical and …

Table 1: Continue.
λemission Turn-on Volt ηEQE
Molecular Structure
(nm) (V) (%)
Blue emitters
White emitters
H 3C

N C 10H 21
- 3.4 0.3
O

4. Conclusion addition, these compounds, with appropriate molecular

engineering, can emit all kinds of hues, even white.
Population growth and technological development have
The emission intensity is enhanced by increasing the
caused a growing need for energy and lighting. A lot of
length of the conjugated system and using electron
research is being done in these two areas to provide
donor and electron acceptor groups. Naphtalimid core
new and low-risk resources. Dyes are one of the main
can be a suitable option for preparing monomers, and
components in the development of photovoltaic and
as a result, luminous polymers. One of the most
electrical technologies. DSSCs and OLED technology
efficient structures in this regard is D-π-A, where the
are two new fields for affordable and available energy
naphthalimide part plays a role as a conjugate bridge or
and lighting. In both of these technologies, dyes play a
an electron acceptor part. However, the search for the
vital role, which produce electricity in the first
preparation of new functional materials with high
(DSSCs) and light in the second (OLED). Because of
efficiency and the introduction of suitable substitutes is
its planar geometry and long conjugated system,
ongoing.
naphthalimide is one of the most important skeletons in
the preparation of materials that are sensitive to light
and electricity. Regarding this structure, it is possible Acknowledgments
to put all kinds of substitutions and electron-donating This work has been supported by the Center for
or electron-withdrawing molecular groups together to International Scientific Studies & Collaborations
obtain the desired hue or emission. The compounds (CISSC), Ministry of Science Research and
prepared with a naphthalimide core have absorption in Technology of Iran..
the visible region and have yellow to violet colors. In

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How to cite this article:

Hosseinnezhad M, Nasiri S, Nutalapati V, Gharanjig K, Arabi AM. A Review of the Application of
Organic Dyes Based on Naphthalimide in Optical and Electrical Devices. Prog Color Colorants Coat.
2024;17(4):417-433. https://doi.org/ 10.30509/pccc.2024.167247.1267.

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