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Diphenylimidazole Based Fluorophores for Explosive Chemosensors

and as Efficient Host Materials for Green Phosphorescent Organic
Light Emitting Diodes
Sandhya Rani Nayak,⊥ Iram Siddiqui,⊥ Shahnawaz, Jwo-Huei Jou, and Sivakumar Vaidyanathan*
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ABSTRACT: Efficient near-ultraviolet light-emitting materials are

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pivotal for organic light-emitting devices (OLEDs) because of their

long lifetime and energy savings for high-quality flat panel displays. In
this study, a series of luminophores having electron-donating and
electron-withdrawing groups with N1 functionalization were designed
that can act as host and chemosensor. All TPTI luminophores show
deep blue emission in the respective phase (solution, thin film, and
solid) with reasonable quantum yield. Electrochemical analysis and
theoretical calculations show a similar trend for HOMO−LUMO
energy gap calculations, and all of them have high triplet energies
(2.76−2.91 eV). High triplet energies of the TPTI luminophores are
extensively applied for green (Ir(ppy)3 2.4 eV) emitting materials. It
has been observed that the host TPTI-1 possesses the highest
efficiency and luminance among all four hosts in all respects at 15.0 wt % with a maximum power efficacy (PEmax) of 24.0 lm W−1, a
maximum current efficacy (CEmax) of 38.2 cd A−1, and a maximum external quantum efficiency (EQEmax) of 6.8% with a maximum
luminance of 7549 cd m−2 at a turn-on voltage of 4.4 V. With their structural functionality, the TPTI luminophores were used for the
recognition of nitro aromatic compounds (including picric acid (PA)). All the luminophores showed good selectivity and high
catching toward the PA, and the sensing mechanism was thoroughly investigated theoretically and experimentally.
KEYWORDS: imidazole, DFT computational, chemosensors, photoluminescence, electroluminescence

■ INTRODUCTION
Organic fluorophores containing a simple framework with
different functional groups have gained enormous importance
because of their easy synthesis and structural modification that
influence the desired properties such as optoelectronics,
chemosensing, organic photovoltaics, etc. in organic flat-
panel flexible displays and solid state lighting products.1−4 In
the latest evolution, the highly decisive phosphorescent organic
light-emitting diodes (PhOLEDs) were emphasized because of
their eminent characteristics to provide nearly 100% internal
quantum efficiency (IQE) by using both singlet and triplet
excitons and outstanding future aspects for the general lighting
applications.5 Even if PhOLEDs could potentially achieve
nearly 100% exciton utilization, the longer lifetimes of triplet
excitons generally lead to poor multiparticle annihilation,
which diminishes the exact efficiencies of these electro-
phosphorescent OLEDs devices.6−8 To effectively suppress
the concentration quenching and triplet−triplet annihilation
(TTA), the phosphorescent dopants are embedded in host
materials, which usually restricts their intermolecular inter-
action.9
Among the combined tactics, the blending frameworks
provide a great deal of scrutiny. It is worth noting that the
highest efficiency PhOLEDs comprise high-carrier-transport
host materials and phosphorescent dyes in the emissive layers
(EMLs). Designing a host matrix having a higher triplet energy
than the phosphorescent dopant is beneficial because it avoids
back-energy transmission from the dopant to the host, which
allows the confinement of excitons. As a result, the host
materials can perform numerous jobs for immensely efficient
PhOLEDs and should fulfill following criteria: (i) they should
confine the triplet excitons and energy transfer through
exothermic process, and the triplet energy of host matrix
should be superior to that of the phosphorescent guest; (ii)
they should properly match the HOMO/LUMO energy level
with that of a neighboring functional layer for efficient charge
injection required for host materials; (iii) they should
appropriately balance the electron−hole mobilites to illustrate
Received: June 25, 2022
Accepted: August 23, 2022
Published: September 6, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsaom.2c00012

94 ACS Appl. Opt. Mater. 2023, 1, 94−106
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Figure 1. Chemical structures (top) diphenyl based luminophores and (down) quenchers used for chemo sensors.
the recombination of the electron−hole within the emitting
layer and to decrease the efficiency roll-off; (iv) they should
extend the lifetime of the devices to fulfill the thermal and
morphological stabilities even though efficient and stable hosts
for PhOLEDs have great challenges for lighting material
research.10,11
It is well-known that to obtain a high-efficiency OLED
device generally requires a multilayer configuration with
functional organic layers to facilitate carrier injection and
transport along with effective exciton confinement. According
to this perspective, the organic chemical structural framework
plays a vital role in the devices and governs their efficiency. To
make the different kinds of functional organic materials, many
functionalized blocks and units have been developed. Across all
functional blocks, imidazole is an important building block that
is primarily used for electron transport and as phosphorescent
host material. Because of their eminent photoluminescence
(PL), electroluminescence (EL) characteristics and easier
modification play a significant role for the establishment and
practical applications of OLED materials. In addition to the
simultaneous realization behavior of OLEDs, chemosensing
properties can be explored because of the existence of a lone
pair in the imidazole derivatives that helps in sensing
nitroaromatic compounds.
Till a recent date, many research efforts have been devoted
to designing small and efficient organic luminescent materials
with ordered molecular structure, unique molecular frame, easy
purification methods, and flexible control of the structural
modification with a simple functional group. They are mainly
focused on the imidazole moiety, which is an important
building block of luminescent materials because of its high
thermal stability and simultaneously realization of chemo-
sensing properties. The electron deficient nature of imidazole
makes it highly polar with an electron-withdrawing nature and
the availability of lone pair on nitrogen helps in sensing
nitroaromatics. Consequently, imidazole based luminophores
(unipolar/bipolar) behave as an electron deficient group,
which benefits the efficient electron transfer in the device. The
unipolar TPI derivatives doped in the CBP host showed
OLED performances of 1.4% of EQE with (0.23, 0.21) CIE
coordinates, which belong to the blue region and also show
promising chemosensing behavior (for picric acid detection).12
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Also, PITTPA shows high thermal stability with high triplet
energy, which are used for green Ir(ppy)3 dopant materi-
als.13,14 The combination of suitable electron rich and electron
deficient moieties in a molecular design result in controlled
energy levels for their ability to transfer holes and electrons
that are introduced simultaneously.15 Hence, designing simple
organic luminophores that show near UV/deep blue emission
in the OLED device is a prerequisite for full color displays.
A novel method was developed for the recognition and
framing of new luminescent materials, which are more
concerned toward the ultralow level detection with a great
effort in the area of chemosensors.16,17 The principal
constituents of chemosensors rely on detecting the most
explosive compounds such as 2,4-dinitrophenol (2,4-DNP),
trinitrotoluene (TNT), and picric acid (PA) with huge
sensitivity. Because of this high sensitivity, these sensors are
attractive for extensive use in public and environmental
protection.18−20 Various rational techniques were refined for
chemosensing.21−23 The chemosensors with excellent photo-
luminescence (PL) property that accomplish fluorescence
quenching by nitro-aromatic compounds with high sensitivity
and selectivity are widely studied. The detection involves both
vapor and solution states at minute concentrations.24−27 π-
Electron-donating characters of small organic molecules are
more sensitive toward the increasing demand of novel
sensor.28,29
Here, we designed and synthesized a series of unipolar
imidazole based simple framework organic fluorophores. Some
of their properties such as photophysical and electrochemical
investigation were carried out in detail. Diphenylimidazole
based fluorophores (TPTI) play the leading role as the
molecular core, and their properties can be regulated by
changing at either the N1 or C1 positions. Thus, the present
study also elaborates the diphenylimidazole core, which is
functionalized with different substituents (electron-withdraw-
ing group (EWG) and electron donating group (EDG)) at the
N1 position (availability of a nitrogen lone pair for the
chemosensing and influence in photophysical properties)
keeping the C1 position fixed as shown in Figure 1. The
synthesized molecules were used as a host for phosphorescent
based OLEDs, and their electroluminescence properties were
studied in detail.
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Figure 2. Optimized structures of diphenyl based luminophores.

■ THEORETICAL CALCULATIONS
To have a better understanding about the electronic properties
donating character and hole-transporting endowment of the
phenyl group, whereas the lowest unoccupied molecular orbital
of the designed diphenylimidazole based fluorophores, the (LUMO) of the luminophores is delocalized over the
ground state geometries were optimized through quantum imidazole and EWG on the TPTI derivatives, as shown in
chemical approach by density functional theory (DFT) with Table 2. This pattern of electron cloud distributions reveals
appropriate functions, as explained in the Supporting their poor intramolecular charge transfer (ICT) leading to
Information (general information for measurements) by their controllable emissions.32
using Gaussian09W30,31 (Figure 2). For the normal mode of
frequencies, the molecular frameworks were observed to be Table 2. FMO Orbitals of the Luminophores (TPTI-1−
positive in the minimum potential energy surface. After the TPTI-5)
energy of ground state (S0) was ratified, the vertical excitation
of the molecules was determined as the first excited state (S1)
energy. UV−visible spectra and the calculations of singlet and
triplet energy levels were calculated by the TD-DFT method.
The optimized geometries in the ground state and their
frontier molecular orbitals (FMO) in the excited state are
listed in Figure 3, and the corresponding data are mentioned in

Figure 3. Energy level diagram of the luminophores (TPTI-1−TPTI-

5).

Table 1. The highest occupied molecular orbital (HOMO) of

electron clouds mostly dispersed over the benzylimidazole
moiety of the TPTI luminophores attributed to the electron-

Table 1. Theoretical Calculations of Diphenyl Based Luminophores (TPTI-1−TPTI-5)

luminophores HOMO (eV) LUMO (eV) HOMO−1 (eV) LUMO+1 (eV) band gap (eV) singlet (eV) triplet (eV)
TPTI-1 −5.39 −1.07 −6.48 −0.88 4.32 3.79 2.91
TPTI-2 −5.35 −1.07 −6.44 −0.84 4.28 3.82 2.91
TPTI-3 −5.67 −2.03 −6.70 −1.37 3.64 3.06 2.76
TPTI-4 −5.55 −1.50 −6.60 −1.32 4.05 3.45 2.89
TPTI-5 −5.63 −1.99 −6.66 −1.47 3.64 3.07 2.88

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Figure 4. UV−visible spectra of luminophores (TPTI-1−TPTI-5) in gas and DCM phase.
The presently designed diphenylimidazole based lumino-
phores, with substitution of EDG and EWG in the N1 position,
have systematically adjusted the energy gap of the HOMO and
LUMO energy levels. The UV−vis spectral calculations were
done by the TD-DFT method in the gas phase and DCM
solvent, as shown in Figure 4. The intense absorption bands
are observed for luminophores because of the π → π*
transitions, and some of them show n−π* transitions of the
imidazole.33 We found that there is no profound change in the
molecular geometries of the luminophores.
Designing host molecules with both efficient injection and
mobility of holes and electrons is essential. The key parameter
is to optimize the design the molecules for enhanced OLEDs.
Injecting both holes and electrons into the molecule to know
the energy barrier was used to estimate the ionization
potentials (IP) and electron affinities (EA).34−36,12 The
transportation of electrons can be interpreted by using the
semiclassical Marcus theory.37 In general, a lower reorganiza-
tion energy resembles a higher charge-transport rate.38 On the
basis of Table ST1, the rate of electron transport is 1 > 2 > 3 >
4 > 5 and the rate of hole transport is 2 > 1 > 5 > 4 > 3. In
addition to comparison with all the luminophore values, the
Δλ values of luminophores 3, 4, and 5 are smaller, revealing
that luminophores 3, 4, and 5 are more potential emitters for
OLED applications. The detailed information about the
charge-transport properties are shown in the Supporting
Information (Table ST1).
■ GENERAL PROCEDURE FOR THE SYNTHESIS OF
FLUOROPHORES
Benzil (1 g, 4.756 mmol), p-toludaldehyde (0.442 g, 4.756
mmol), ammonium acetate (3.662 g, 47.56 mmol), and an
equivalent amount of amine derivatives in the presence of
ammonium acetate were added to 25 mL of acetic acid
(Scheme 1). For 12 h, the mixture was refluxed. It was cooled
after completing the reaction at room temperature. The
reaction product was resettled into ice water, and consec-
utively, the organic compound was withdrawn from DCM.
Then, adding silica gel to the extracted organic compound
generated a crude product. By column chromatography (ethyl
acetate:petroleum ether (3:7), v/v) the white solid product
was separated out. The complete study of NMR and mass
spectral analysis is shown in the Supporting Information
(Figures S1−S10).
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Scheme 1. Synthetic Procedure of the Designed
Fluorophores
■ RESULTS AND DISCUSSION
Thermal Properties
Thermal study of the synthesized fluorophores was done by
thermogravimetric analysis (TGA) with a heating rate at 10
°C/min under a nitrogen atmosphere. TGA curves reveal the
temperature degradation of 5% weight loss of the fluorophores
are 293 °C (TPTI-1), 300 °C (TPTI-2), 287 °C (TPTI-3),
250 °C (TPTI-4), and 276 °C (TPTI-5) above the
sublimation temperature, resulting in good thermal stability.
All the fluorophores shown in Figure 5a have comparable
decomposition temperatures because of their similar molecular
frameworks.39,40 Figure 5b displays the DSC curves of heating
scans at 10 °C/min, which show the exact Tg values of
materials. It is seen that the glass transition of fluorophores was
observed at rather high temperatures from 148 to 230 °C, and
no peaks because of crystalline and melting appeared during all
the experiments; i.e., the materials are well suited for the
formation of amorphous layers.41,42 Therefore, the prerequisite
criteria for highly efficient smart OLEDs is the thermal stability
of the materials, and to prevent crystallization of the
amorphous films, the glass transition temperature should be
above 100 °C.43−45
Photophysical Properties
Figure 6a depicts the UV visible absorption spectra of newly
synthesized luminophores (TPTI derivatives) in dichloro-
methane (CH2Cl2). The spectra of the luminophores show two
absorption peaks at ∼232−300 nm. The absorption peak of all
the fluorophores around 232 nm may be allocated to the
typical π−π* transition of electrons in the phenyl ring,
signifying they have the same conjugation backbone.46,47 The
absorption peak at ∼284−300 nm is from the π−π* transition
of electrons in the phenyl ring attached with the N atom of the
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Figure 5. (a) TGA curves and (b) DSC curves of fluorophores at a heating rate of 10 °C/min in nitrogen atmosphere.

Figure 6. (a) UV−visible absorption spectra and (b) phosphorescence spectra of synthesized luminophores (TPTI-1−TPTI-5).

Figure 7. Excitation and emission spectra of TPTI luminophores in the solution phase.

imidazole ring. To examine the lowest excited singlet state (S1)
and lowest excited triplet state (T1) of the luminophores, PL
spectra in DCM solutions, solid and thin film matrixes have
also been measured simultaneously (Figures 7−9 and Figure
6b). Here the corresponding data are tabulated in Table 3. All
TPTI fluorophores show near UV/deep blue emission in
solutions, solids, and thin films with the maximum emission
peaks ranging from 370 to 401 nm. The introduction of
functional groups, such as attachment of electron-withdrawing
and electron-donating groups to the imidazole core, increases
the conjugation. Interestingly, attaching the electron-with-
drawing group to the imadzole ring gives a bathochromic shift,
from which it may be concluded that the withdrawing moiety
could have slighty influenced the fluorescence emission
98
wavelength.48 However, we observed a red shift (approx-
imately 10 nm) in the case of TPTI-3, TPTI-4, and TPTI-5,
which is because of the presence of EWG of the fluorophores.
Generally, all the fluorophores show ultraviolet/deep blue
emission. The low-temperature PL emission spectra are
measured. The spectra of the luminophores exhibited around
415−430 nm (TPTI-1 (415 nm, 2.98 eV), TPTI-2 (415 nm,
2.98 eV), TPTI-3 (424 nm, 2.92 eV), TPTI-4 (420 nm, 2.95
eV), and TPTI-5 (423 nm, 2.93 eV)), and their triplet energies
are well aligned with the theoretical calculations. Some of the
corresponding CIE color coordinates are mentioned in Figure
10. All the luminophores show PL quantum yields in the range
14−47.4%, comparable to values for TPTI-4, which shows a
higher quantum yield (47.4%) because of the presence of a
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Figure 8. Excitation and emission spectra of TPTI luminophores in the solid phase.

Figure 9. Excitation and emission spectra of TPTI luminophores in the thin film.

Table 3. Photophysical and CIE Chromaticity Values of All TPTI Luminophores

λem (nm) PLQY (Φ) (%) CIE coordinates (x, y)
TPTI derivatives λabs (nm) solution PMMA film solid S1 (eV) T1 (eV) solution solution PMMA film solid
TPTI-1 233, 284 380 371 365 3.26 2.98 14.00 0.160, 0.018 0.162, 0.014 0.162, 0.014
TPTI-2 234, 288 381 376 376 3.25 2.98 30.80 0.160, 0.018 0.162, 0.013 0.162, 0.013
TPTI-3 232, 296 388 394 401 3.19 2.92 44.30 0.157, 0.023 0.160, 0.016 0.160, 0.016
TPTI-4 233, 300 388 382 381 3.19 2.95 47.40 0.195, 0.020 0.162, 0.013 0.162, 0.013
TPTI-5 234, 290 385 388 385 3.22 2.93 43.10 0.158, 0.209 0.162, 0.013 0.161, 0.014

Figure 10. CIE color coordinates of TPTI luminophores in the solution phase, solid phase, and thin film.

strong EWG at the m-CF3 substituted phenyl ring. The digital
spectra of luminophores in solutions, solids, and a PMMA
matrix are depicted in Figures 7−9.
Chemosensing Properties
The sensing behaviors of diphenylimidazole luminophores for
PA were investigated by using fluorescence spectroscopy. All
the luminophores were dissolved in THF (1 × 10−5 M) and
99
examined. Furthermore, a set of different explosive compounds
such as phenol (PH), benzoic acid (BA), 4-nitrophenol (4-
NP), 2,4-DNP, and PA were added into the solution to study
the variation in the fluorescence (FL) intensity of the
luminophores. Upon subsequent addition of quenchers in
the solutions, as shown in Figure 11 and Figure 12, the
emission intensity of the luminophore observes to be
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Figure 11. Variation in the emission of TPTI-1 upon the gradual addition of PH, BA, 4-NP, and 2,4-DNP.

Figure 12. (a) Variation in emission intensity of TPTI-1 upon the gradual adding up PA. (b) Stern−Volmer plots of TPTI-1 using quencher as a
PA.

decreased. The quenching constant (KSV) was calculated with
the help of the Stern−Volmer equation.
I0/I = 1 + KSV[Q]
where I0 stands for the initial FL intensity and I stands for the
intensity after subsequent addition of PA and [Q] denotes the
concentration of quencher. The variation in FL intensity and
the Stern−Volmer plots (I0/I vs PA concentration) of all the
fluorophores (TPTI-2−TPTI-5) are shown in the Supporting
Information (Figures S19−S26). The K SV of all the
luminophores were calculated between 1.81 × 104 and 7.17
100
× 104. All the Stern−Volmer plots illustrate the super amplified
quenching effect because of upward bending curves. Again, it is
observed that with the increasing concentration of PA, the
luminescence quenching becomes more efficient toward PA. At
a lower concentration of PA, the Stern−Volmer curve was
linear, signifying that the static quenching interaction between
the luminophore and PA occurs. Moreover, the digital spectra
clearly indicate that the color of fluorescence changed from
blue to colorless whereas other nitro-aromatic compounds
showed a relatively lower decrease in fluorescence efficiency as
compared to that for PA.
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Figure 13. 1H NMR spectra of TPTI-1 without and with 0.5 and 1.0 equiv of PA in CDCl3.

The probable mechanism for the detection of PA is depicted

in Figure 13, where a fall in the emission intensity of
fluorophores was observed because of the stronger acidic
behavior of PA. Therefore, the acidic proton easily gets
attracted toward the imidazole nitrogen atom. The emission
quenching happens because of the strong interaction of the
lone pair of the imidazole N atom with acidic PA. Such an
interaction was proved by 1H NMR spectroscopy, as illustrated
in Figure 13 and Supporting Information (Figures S15−S18).
The 1H NMR peak of PA is shifted to a lower chemical shift
value (δ, ppm), which confirms the formation of a complex
between the diphenylimidazole N atom and PA. Upon
addition of excess of PA, the PA proton signal moves further
upfield, supporting the firm electrostatic interaction between
PA and the luminophores. This result suggests that the Figure 14. Process of electron transfer of TPTI-1 to TPTI-5 and PA
photoinduced electron transfer (PET) process may play a vital by DFT.
role in the FL sensing mechanism. The lifetime of the
respective luminophores in the presence and absence of PA summarized in the Supporting Information (Figures S11−
and their corresponding data are shown in Figure S27 and S14).
Table ST2 in the Supporting Information. Figure 16 diplays
the images of a solution of fluorophores under a UV lamp (365
nm) after addition of PA.
Detection Mechanism of PA by DFT Study. Further-
more, for better understanding of PA sensitivity, the FMO of
PA and TPTI derivatives (TPTI-1−TPTI-5) were verified by
DFT. The LUMO and HOMO energies of PA were estimated
to be −4.52 and −8.58 eV, respectively. These values lie
between the calculated energies of the luminophores (TPTI-
1−TPTI-5). According to Figure 14, the PET process may be
the principle cause of emission quenching of luminophores.
Additionally, attachment of PA to the luminophores confirmed
the ICT process through a FMO study. Herein, for all the Figure 15. Process of electron transfer of TPTI-1 and PA by DFT.
fluorophores, the electron density mainly distributed over the
phenyl groups of the luminophores in the case of the HOMO
whereas the LUMO dispersed over the imidazole groups of the
luminophores. The moment when the PA is attached to the Detection Limit of PA. The detection limit (DL) was
luminophores, the HOMO is dispersed over the luminophores calculated by calibrating the FL intensity of all luminophores
whereas the LUMO is dragged toward PA. Hence, PA binding along with PA in 10−6 M THF solution. The respective FL
with the luminophores results in a decrease in energy, which intensity against the PA concentration is illustrated in Figure
evidences the formation of a strong interaction of PA with the 17. The DL can be calculated by the help of eq 1.49
luminophores.25 The FMO orbitals of TPTI-1 with PA are
illustrated in Figure 15 and for TPTI-2 to TPTI-5 are DL = C L × CT (1)

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Figure 16. Images of a solution of fluorophores under UV light after adding PA.

Figure 17. Fluoroscence intensity against PA concentration of luminophores.

Figure 18. Cyclic voltammetry curves of diphenyl based luminophores.

C L represents the concentrations of luminophores; C T
represents the concentrations of PA at which a sudden
decrease is observed. The DL of all luminophores observed
between 145 and 198 ppb, and the values are given in Table
S3. Among all, TPTI-2 showed more sensitivity toward PA
102
because of the presence of a methyl unit as an EDG, enabling
more interaction with electron deficient PA.50
Electrochemical Analysis. For OLED application charge-
injection/-transport mechanism, the HOMO and LUMO
energy levels are foremost requirements.46,51 To estimate the
HOMO and LUMO energy levels, cyclic voltammetry (CV)
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analysis was carried out to evaluate the redox active behavior of structure, anode and cathode materials are indium tin oxide
TPTI derivatives. The respective CV curves are shown in (ITO) and aluminum (Al). The hole-injection/-transport
Figure 18, and their relevant data are summarized in Table 4. material is poly(3,4-ethylenedioxythiophene)−poly-
(styrenesulfonate) (PEDOT:PSS) and host materials are
Table 4. Electrochemical Analysis of Diphenyl Based TPTI-1, -3, -4, and -5 taken individually. The electron-
Luminophores injection and -transport materials are lithium fluoride (LiF)
and 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBi),
Eox Ered EHOMO ELUMO Eg
luminophores (V)a (V)a (eV) (eV)b (eV)b respectively.
The electroluminescent properties of the fabricated OLED
TPTI-1 1.77 −1.52 −6.17 −2.88 3.29
device are studied and tabulated in Table 5 showing the best
TPTI-2 1.40 −1.54 −5.80 −2.86 2.94
device performances for the host TPTI-1, -2, -3, -4, and -5
TPTI-3 1.65 −1.33 −6.05 −3.06 2.99
doped in Ir(ppy)3. Its corresponding current density−voltage−
TPTI-4 1.43 −1.63 −5.83 −2.76 3.07
luminance (J−V−L) characteristics and efficiencies are
TPTI-5 1.67 −1.46 −6.07 −2.93 3.14
a onset
displayed in Figure 20. All the host based devices are
Ered = the onset reduction potentials; Eonset
ox = the onset oxidation optimized concerning different dopant concentrations varying
potentials. bELUMO = −e(Eonset
red + 4.4); Eg = band gap = EHOMO − as 10.0, 12.5, 15.0, and 17.5 wt % (Supporting Information
ELUMO.
Figures S28−S32 and Table ST3). It has been observed that
the host TPTI-1 possesses the highest efficiencies and
The HOMO energy levels could be figured out from the onset
luminance among all the four hosts in all respects at 15.0 wt
oxidation potentials by the well-known equation HOMO =
% with a maximum power efficacy (PEmax) of 24.0 lm W−1,
−(4.4 + Eox) (eV). Consequently, the LUMO can be
maximum current efficacy (CEmax) of 38.2 cd A−1, and
calculated by LUMO = HOMO + Eg (eV), where Eg
maximum external quantum efficiency (EQEmax) of 10.1% with
represents the optical band gap. The calculated HOMO level
a maximum luminance of 7549 cd m−2 at a turn-on voltage of
follows the same trend as predicted by DFT calculations
4.4 V. This result may be attributed to the deep HOMO level
(similar HOMO distributions). TPTI luminophore HOMO
that provides a large hole barrier resulting in the transportation
values are found to be −6.17, −5.80, −6.05, −5.83, and −6.07,
of the maximum number of holes into the emissive layer
respectively, and their LUMO energy are found to be −2.87, (EML). Additionally, an electron barrier of 0.17 eV restricts
−2.85, −3.06, −2.76, and −2.93, respectively. the flow of electrons toward HIL/HTL enhancing the density
Electroluminescence Properties. The enormously large of electrons in EML for maximum recombination. This barrier
bandgap, suitable molecular orbital levels, and sustainable also helps to attain a better efficiency at high luminance, which
thermal properties of TPTI-1, -2, -3, -4, and -5 materials is seen in our case.
encouraged us to use them in applying OLEDs as host Figure 20 shows the electroluminescent (EL) characteristics
materials. The emitter is chosen to enable the maximum of OLED devices comprising all four host TPTI-1, -3, -4, and
energy transfer based on its matching HOMO−LUMO and -5 doped with Ir(ppy)3 at 15.0 wt %. Figure 20a displays EL
triplet energies. Phosphorescent green dopant Ir(ppy) 3 spectra peaked at around 520 nm, verifying the green emission
possesses a HOMO and a LUMO of −5.6 and −3.0 eV, from the phosphorescent green dopant. The single peak
respectively, which, in comparison to the host material values, suggests the efficient host−guest energy transfer. Figure 20b
gives a difference of 0.2−0.5 eV for the LUMO and 0.1−0.3 eV displays the CIE chromaticity charts pointing at the CIE
for the HOMO levels. The triplet energies are also near the coordinated for the obtained OLED devices and their
difference range 0.3−0.5 eV, in comparison to the host’s triplet corresponding EQEmax values. The CIE coordinates of these
energy. Furthermore, a device structure is designed as shown in devices lie between (0.31, 0.62) and (0.32, 0.61), indicative of
Figure 19 and comprises anode (125 nm)/HIL (35 nm)/ a null shift. Figure 20c displays the J−V−L characteristics
host:Ir(ppy)3 (x wt %; x = 10.0, 12.5, 15.0, 17.5) (20 nm)/ suggesting the highest luminance. Figure 20d shows the CE−
ETL (40 nm)/EIL (1.0 nm)/cathode (200 nm). In this luminance−PE plot indicating the maximum CE and PE
achieved using host material TPTI-1. Among all, the TPTI-4
based device showed low luminance, and it may be attributed
to formation of charge traps and insufficient charge-carrier
balance between injected electrons and holes in the emissive
region. Moreover, recombination of free electrons with trapped
holes might have resulted in the nonradiative quenching
processes between excitons and hole traps.52−56

■ CONCLUSION
In the present investigation, five efficient diphenylimidazole
based organic luminophores with electron-donating/-with-
drawing moieties (different R groups) were synthesized. All
luminophores showed reasonable quantum yields, and a
detailed photophysical study revealed that the fluorophores
emitted in the near UV to deep-blue region. The fluorescence
quenching occurred sensitively and selectively after attaching
Figure 19. Schematic energy level diagram displaying host materials picric acid. The sensing mechanism enactment of the TPTI
TPTI-1, -2, -3, -4, and -5 using green phosphorescent dopant based luminophores was verified both experimentally and
Ir(ppy)3. theoretically. Compared with other nitroaromatics, PA showed
103 https://doi.org/10.1021/acsaom.2c00012
ACS Appl. Opt. Mater. 2023, 1, 94−106
ACS Applied Optical Materials pubs.acs.org/acsaom Article

Table 5. Electroluminescent Properties of the Host TPTI-1, -2, -3, -4, and -5 at 15 wt % Concentration of Green Dopant
Ir(ppy)3
Ir(ppy)3 doping turn-on PE100/CE100/EQE100 (lm PE1000/CE1000/EQE1000 PEmax/CEmax/EQEmax (lm CIExy maxi lum
host conc (wt %) voltage (V) W−1/cd A−1/%) (lm W‑1/cd A−1/%) W−1/cd A−1/%) coordinates (cd m−2)
TPTI-1 15 4.4 15.5/22.2/6.8 10.2/21.1/6.7 24.0/22.2/6.8 (0.31, 0.62)/ 7549
(0.31, 0.62)
TPTI-2 15 5.6 6.3/13.2/3.7 4.7/12.7/3.3 6.5/14.6/4.2 (0.32, 0.61)/ 7996
(0.32, 0.61)
TPTI-3 15 4.5 5.3/8.5/2.3 7.5/10.1/2.7 (0.32, 0.61)/− 894
TPTI-4 15 5.5 1.5/3.2/0.7 4.2/6.7/1.3 (0.32, 0.61)/− 366
TPTI-5 15 4.9 6.9/11.1/2.9 11.6/14.7/4.0 (0.32, 0.61)/− 1199

Figure 20. (a) Electroluminescence spectra, (b) CIE chromaticity spectrum diagram, (c) current density−voltage−luminance, and (d) current
efficacy−luminance−power efficacy plots of the host TPTI-1, -3, -4, and -5 with 15 wt % of green dopant Ir(ppy)3.

more quenching efficiency. The detection limit of the TPTI

fluorophores was in the range 145−198 ppb. Furthermore, we
investigated the effect of these luminophores as a host material
for PhOLED device performance. TPTI-1 showed the best
performance with a PEmax of 24.0 lm/W, a CEmax of 22.2 cd/A,
and an EQEmax of 6.8% when doped with the green dye (at
12.5 wt %) Ir(ppy)3. As seen from the EL spectra, the efficient
host-to-guest energy transfer took place with a pure green
emission at ∼520 nm with no other side peaks.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaom.2c00012.
Experimental section, characterization data, NMR, mass,
fluorescence, and electroluminescence spectra, DFT,
electron transfer process, lifetimes, OLED device
fabrication and characterization, and Cartesian coor-
dinates (PDF)
104
■ AUTHOR INFORMATION
Corresponding Author
Sivakumar Vaidyanathan − Department of Chemistry,
National Institute of Technology Rourkela, Rourkela 769 008
Odisha, India; orcid.org/0000-0002-2104-2627;
Phone: +91-661-2462654; Email: vsiva@nitrkl.ac.in
Authors
Sandhya Rani Nayak − Department of Chemistry, National
Institute of Technology Rourkela, Rourkela 769 008 Odisha,
India
Iram Siddiqui − Department of Materials Science and
Engineering, National Tsing Hua University, Taiwan 30013,
ROC
Shahnawaz − Department of Materials Science and
Engineering, National Tsing Hua University, Taiwan 30013,
ROC
Jwo-Huei Jou − Department of Materials Science and
Engineering, National Tsing Hua University, Taiwan 30013,
ROC
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaom.2c00012
https://doi.org/10.1021/acsaom.2c00012
ACS Appl. Opt. Mater. 2023, 1, 94−106
ACS Applied Optical Materials
Author Contributions
⊥ Miyamoto, H.; Kajita, T.; Kakimoto, M. Spin-Coated Highly Efficient
S.R.N. and I.S. contributed equally.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
V.S. strongly acknowledges SERB, DST, India (EMR/2016/
002462), and Ministry of Science and Technology (MOST),
Taiwan, for experimental support.
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