Journal(of(Materials(and(( J. Mater. Environ. Sci.

, 2019, Volume 10, Issue 3, Page 195-207

Environmental(Sciences(
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Designing New Small Molecules from Cyclopentadithiophene (CPDT)

Derviatives for Highly Efficient Blue Emitters in OLEDs: DFT
Computational Modeling
Rania ZAIERa, Said HAJAJIa, Masatoshi KOZAKIb and Sahbi AYACHIa
a
Laboratory of Physico-Chemistry of Materials (LR01ES19), Faculty of Sciences of Monastir (FSM), Avenue of the
environment 5019 Monastir, University of Monastir, Tunisia.
b
Laboratory of Physical Organic Chemistry, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto,
Sumiyoshi-ku, Osaka 558-8585, Japan

Received 12 May 2019, Abstract

Revised 15 May 2019,
Novel blue florescent emitters of two types of linear π-conjugated molecules based on the
Accepted 15 May 2019
cyclopentadithiophene (CPDT), having the same backbone but bridging positions with
>C=O (D1) or >C=C(CN)2 group (D2) are designed and theoretically studied.
Keywords Calculations of the molecular properties of the dimers (D1 and D2) were performed in
!!CPDT, both ground and excited states using the density functional theory (DFT) and its time-
!!DFT, dependent extension (TD-DFT) at B3LYP functional with 6-311g(d,p) basis set in
!!Electronic properties, acetonitrile. The optical properties have been computed and data related to their responses
!!ICT, are examined and interpreted. The direct comparison between both dimers highlights the
!!OLED. effect of carbonyl (>C=O) bridged groups on emission quenching. In addition, intra-
molecular charge transfer (ICT) band in the visible region (~672 nm) was detected for D1,
in contrast to D2. The ICT is strongly implicated as the quenching emission caused by the
[email protected]; electron-donating (>C=O) group for D1. In the three layers based OLED
Phone: +216 73500274; [ITO/NPD/emitting layer (D1 or D2)/Alq3/LiF:Al], the electric responses of the devices
Fax: +21673500278 were evaluated based on the I-V characteristics. Our theoretical results suggest that the
CPDT derivatives have interesting optical properties, which are useful for constructing
novel light emitting materials for OLEDs.

1.( Introduction
Research efforts, over the past several decades, have been devoted to the advancement of organic
conjugated systems by an appropriate chemical modification [1-4]. The development of new methodology for
the synthesis of short chains, oligomers and polymers gives specifically designed properties for their
applications in optoelectronic devices (organic light-emitting diodes (OLEDs) [5-10] and organic solar cells
[11-14]). Unfortunately, most OLEDs emitters are still not satisfactory. Therefore, the design and synthesize for
new emitting materials with high efficiency have always been one of the biggest challenges in organic
electronics [15-18].
Numerous studies have demonstrated that donor-acceptor conjugated systems offer a rational tailoring of the
electro-optical properties by the adjustment of the donor (push of electron) and acceptor (pull of electron) units
[19-22]. As an effective building block, 4H-cyclopenta[2,1-b:3,4-b’]dithiophene (CPDT) has been exploited for
constructing the π-conjugated skeleton of organic applications due to its excellent co-planarity and photo-
induced electron transfer capability [23, 24].
As a continuation of our previous work [25], we have theoretically studied the CPDT derivatives with two
different substituents on the bridging positions to obtain defined and linear π-conjugated systems with small
optical band gaps. Connection with electron-donating and accepting groups has been undertaken to control the

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fundamental optoelectronic properties of compounds. In other cases, a great deal of attention has therefore been
focused on the supramolecular organization in organic conjugated materials by controlling their electronic
parameters (optical band gap, energy levels of the highest occupied molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO), effective conjugation length, etc) for desired electronic applications
[26].
In order to probe the properties that are difficult to measure and to provide new links necessary for the
understanding of the structure-property relationships of materials, the theoretical approach was used as a helpful
tool to understand specific phenomena. It also helps scientists make predictions before running the actual
experiments. Indeed, theoretical calculations based on the density functional theory (DFT) constitute not only an
ideal compromise tool but also an essential analysis method in the same way as other spectroscopic methods of
analysis.
Our previous works [25, 27,28] suggested that the DFT/B3LYP method with the 6-311g(d,p) basis set, in
solution medium, was reliable for optimization of conjugated systems and its TD-DFT was practical for optical
properties simulation.
The current study provides a comparative theoretical analyses related to the optical and electronic
properties of organic conjugated homo-dimers containing the 4H-cyclopenta[2,1-b:3,4-b’]dithiophen-4-one and
the 2-(4H-cyclopenta[2,1-b:3,4-b']dithiophen-4-ylidene) malononitrile. The dimers under study are, henceforth,
referred to as D1 and D2, respectively.

Scheme 1: Molecular structures of D1 (a) and D2 (b).

Calculations of molecular properties were performed in both ground and excited states of D1 and D2, in
acetonitrile. The vertical excitation energies and oscillator strengths of the first three transitions were computed.
In a second step, TD-DFT approach was used to simulate the optical absorption and emission spectra in their
respective states. This leads to a consistent and helpful interpretation of the intra-molecular charge transfer
(ICT) properties as well as the theoretical design of OLED based D1 or D2 as emitting layer. To investigate the
charge transport properties, we have calculated the reorganization energies for electron (λ" ) and for hole (λ# )
which are a measure of structural change between ionic and neutral states. We have also calculated the electron
density difference (EDD) maps which represent the variation of electron density caused by the charge transfer
interactions.

2.( Computational details

To perform a theoretical survey on the target OLEDs, some electronic descriptors such as the energy levels
of the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and the
energy gap between these molecular orbitals (MOs) have been computed and compared. All the calculations
were performed with the Gaussian 09 software [29]. Theoretical calculations for the dimer molecules (D1 and
D2) were performed based on the DFT. Internal reorganization energy refers to the energy required for the
geometry relaxation when going from the neutral state to a charged molecular state and vice versa [30].
Based on calculations on optimized geometries of the electric neutral, cationic and anionic charged states of
the dimer compounds, electronic parameters including the adiabatic ionization potential (IPa), adiabatic electron
affinity (EAa) and the reorganization energies were evaluated using the DFT/ B3LYP method with the 6-
311g(d,p) basis set, in acetonitrile medium using the conductor-like polarizable continuum model (CPCM).
These electronic parameters are an important task to tune the carrier’s injection efficiency for OLEDs.

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 To evaluate the frontier molecular orbitals (FMOs), the ground (S0) and lowest singlet excited (S1) states
geometries of the compounds are optimized by DFT/B3LYP at 6-311g(d,p) and configuration interaction singles
(CIS) methods, respectively. Absorption and emission spectra of both dimers have been calculated at the TD-
B3LYP level using the 6-311g(d,p) based on the S0 and S1 optimized geometries, respectively.
International Commission on Illumination CIE was used to obtain emission colors coordinates. Finally, the
I-V characteristics of OLED devices based dimer (D1 or D2), as emitting layer, have been simulated using
SILVACO software [31].

3.( Results and discussion

3.1.(Geometry changes in excited states
First of all, we can find that both compounds have symmetrical structure and revealed co-planarity
between units due to intra-molecular atomic interaction like hydrogen bonds, as depicted S---H (Scheme 2). The
highly planar structures due to the presence of intra-molecular non-covalent interactions can apparently increase
the rigidity of the molecular backbone [32]. Further, both CPDT structures remain planar in their excited states.

Scheme 2: Optimized geometry of CPDT dimers.

The S-C-C-S dihedrals are obtained to be 179.9° (planar structures) for both D1 and D2. The intra-
molecular interactions taking place within the molecular structures generate self-rigidification that improves π-
electron delocalization over the conjugated chains. Non-covalent bond lengths of S---H at ground state are
found to be 2.91 Å for D1 and 2.93 Å for D2 which are rather less than the sum of the van der Waals radii for S (1.80
Å) and H (1.20 Å) at 3.00 Å [33,34]. Moreover, we found that the most sensitive modes to S---H interactions are
located approximately at 47 cm-1 for D1 and 34 cm-1 for D2.
As depicted in Table 1, the dipole moment of both dimers is nearly zero due to the high symmetry of the
molecular structures. However, only D2 exhibits higher dipole moment upon excitation, the value is found at
about 4.6 Debye that arise from the efficient bridging group effect. The total energies of D1 and D2 at optimized
geometries are found to be -2432.96 and -2730.15 Hartree, respectively, indicating that D2 is more stable
regarding the high conjugation of this latter.

Table 1: Calculated total energy and dipole moment at B3LYP/6-311g(d,p) level of dimers at their ground (S0) and excited
(S1) states

Compounds Total Energy (Hartree) Dipole Moment (Debye)

D1 -2432.96 (GS) 0.0009 (GS)

-2424.98 (ES) 0.0002 (ES)
D2 -2730.15 (GS) 0.0026 (GS)
-2720.29 (ES) 4.645 (ES)

The different bond lengths of the studied compounds in optimized ground and excited states geometry are
illustrated in Fig. 1a (D1) and Fig. 1b (D2). As it can be seen, there is a slight discrepancy in terms of bond lengths
between ground and excited states as a result of modification in electron delocalization within the molecular structures.
Particularly, the bond length as numbered 14 (linkage between the two CPDT subunits) is dramatically reduced to
form a double bond favoring the ICT between subunits. It is not surprising therefore that upon electronic
excitation molecules may adopt equilibrium geometries very different from those in their ground states.

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 Fig. 1: Bond lengths at optimized ground and excited states of D1 (1a) and D2 (1b).

In addition, C=O bond has shortened upon excitation (1.21 Å→1.19 Å) giving an electronic n→π*
transition (see after band at 672 nm). From the calculated energies for the excited S1 states, we can deduce that
geometries are slightly decreased in stability regarding their ground S0 states.

3.2.(The Frontier Molecular Orbital (FMO) energy levels and band gaps
To further determine the energy levels of frontier orbitals, Fig. 2 illustrates the electronic energy level
diagrams of the studied dimers as well as their FMOs in the ground states. We conclude that the HOMO
electrons in both dimers are predominantly distributed on the entire framework of the CPDT, expect
contributions from the bridging groups. This result implies that such systems can be considered as highly
conjugated configurations. On the other hand, the LUMO electrons are delocalized over whole dimer molecules
and the good overlap between subunits can facilitate the electron migration.

Fig. 2: Frontier molecular orbitals (FMOs) and energy levels at ground state using DFT/B3LYP/6-311g(d,p) method.

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 In excited states of dimers, we find that no appreciable changes of FMOs were detected for D1.
Unfortunately, in the case of dimer D2, exclusively one of CPDT moiety contributes to the LUMO orbital (see
Fig. 3), thanks to electron acceptor character of >C=C(CN)2 group.

Fig. 3: Frontier orbitals illustrated at the optimized ground (S0) and excited (S1) state geometries of the dimers molecules
obtained DFT// and TD-DFT//B3LYP/6-31g(d,p) levels of theory, respectively.

The optical energy gap separating the HOMO/LUMO energy levels of D1 and D2 are calculated and
illustrated in Table 2. We deduce that relatively small optical gap was obtained in the case of D2 (1.91 eV)
compared to D1 (2.38 eV). Since the HOMOs have a nodal plane at the bridging carbon atom in the CPDT,
electron withdrawing groups at the bridging carbon selectively stabilize the LUMOs. This is a reason for the
narrow band gaps of these compounds.

Table 2: Calculated energetic parameters at DFT//B3LYP/6-311g (d,p) level.

Compunds εHOMO (eV) εLUMO (eV) ∆E&'( (eV) εHOMO-1 (eV) εHOMO+1 (eV)
D1 -5.36 -2.98 2.38 -6.51 -2.82
D2 -5.51 -3.60 1.91 -6.65 -3.58
The FMOs analysis has turned out that the vertical electronic transitions of absorption and emission of
both dimers are characterized as ICT [35, 36]. This latter arising from the electron transition from the HOMO to
the LUMO indicates the formation of charge density difference between ground (S0) and excited (S1) states that
can be visualized through the electronic density difference (EDD) plots. The major changes in EDD, which are
reflected in atomic charges, should be apparent in the molecular electrostatic potential (MEP) that derived an
analysis of electron density. Here, the EDD plots of the studied compounds have been illustrated in Fig. 4. As
displayed in the figure, the regions of the electron density depletion presented in blue color are mostly localized
at the donor parts, while the regions of the electron density increment presented in purple color are largely
aligned with the acceptor parts [37,38].

Fig. 4: Electron density difference (EDD) isosurface maps between ground (S0) and excited (S1) states of D1 and D2.

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3.3. Molecular Electrostatic Potential (M.E.P) Maps and Mulliken population analysis
The Mulliken charges and surface electrostatic potentials usually shed light on the electron distribution and
electrostatic interaction within molecules. Therefore, molecular electrostatic potential (M.E.P) is a useful
descriptor for understanding the reactive sites of electrophilic and nucleophilic attacks of the studied molecules
as long as it is directly related to the electron density [39]. To predict the different reactive sites of D1 and D2,
the M.E.P calculated at B3LYP/6-311g(d,p) at optimized geometries have been simulated and depicted in Fig. 5.
The negative regions of M.E.P, represented in red color, are referring to electrophilic reactivity and the positive
regions that are produced in white color are related to nucleophilic attack. In ground states of dimers, the
symmetric charge distribution gives a partially positively charge CPDT and a negatively charged bridging
groups (in periphery).

Fig. 5: Molecular electrostatic potential surface (MEP) of D1 and D2.

To make easy the interpretation of the charge distribution, we have calculated the Mulliken atomic charges
over the different molecular domains for the two CPDT molecules (Fig. 6). It is worth remembering that the
two CPDT structures with symmetric geometries are planar. Here, the net charges over the CPDT moiety and
bridging groups are also identical in their ground states, but affected upon excitation.

As shown, in their ground states, the partial negative charges are on the >C=C(CN)2 bridging groups. In
turn, the partial positive charges are spread on the CPDT backbone, for both dimer molecules. When regarding
excited states of molecules, a redistribution of electronic charges was detected. The arrangements can
potentially result in a strong π-π interaction within the CPDT fragments. These results show qualitative
agreement with the results based on the FMOs analysis.

Fig. 6: Mulliken atomic charges distribution at ground (S0) and excited (S1) states of D1 and D2.

3.4. Optical responses (UV-Vis-NIR optical absorption and emission)

The absorption properties of the titled compounds based on UV-Vis-NIR spectra are displayed in Fig. 7.
The data related with their behaviors are listed in Table 3. First of all, the UV-vis-NIR spectra have three
distinct absorptions peaks appeared at 312, 372 and 672 nm for D1. However, the detected peaks are red-shifted
and appeared at 359, 394 and 946 nm for the D2.

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 Fig. 7: Simulated optical absorption spectra of dimer molecules at TD-DFT//B3LYP/6-311g(d,p) level of theory.

Table 3: The vertical excited energies (nm) and their oscillator strengths for the ground (S0→S1) states of dimers by
TD//B3LYP/6-311g(d,p) level of theory.

Compounds λ+,-
)'* (nm) E(eV) f (a.u) Main Transition
D1 312 3.97 0.4099 H-4 L (55%)
394 3.33 0.7592 H L+2 (93%)
672 1.84 0.3026 H L (96%)
D2 359 3.47 0.7434 H-2→L+1 (28%)
394 3.08 1.0941 H→L+2 (93%)
946 1.31 0.0780 H→L (96%)

Additionally, compared to D2, a dramatic hypo-chromic effect was observed in UV-vis-NIR spectrum
of D1. Logically speaking, the changes are closely related to their molecular properties arising from electron
withdrawing and donating group’s effect. We will return later to this point. For D2, the selective stabilization of
the LUMO by the bridging groups is important. Then, the stronger electron withdrawing group gives stronger
stabilization effect. The simulation of resolved emission spectra is illustrated in Fig. 8. The corresponding
emission properties are summarized in Table 4.

Fig. 8: Simulated emission spectra of dimer molecules at TD-DFT//B3LYP/6-311g(d,p) level of theory.

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Table 4: The vertical emission energies (nm) and their oscillator strengths for the first excited (S1→ S0) states
of dimers by TD//B3LYP/6-311g(d,p) level of theory.

Compounds λ0)
)'* (nm) E123 (eV) f (a.u) Main Transition τ (ns)

D1 319 3.88 0.2147 L H-5 (81%)

419 2.96 0.7543 L+2 H (95%) 3.49

831 1.50 0.4528 L H (97%)

D2 334 3.5987 0.2351 L+1 → H-3 (51%)

389 3.1061 0.4341 L → H-2 (42%)
448 2.7426 0.8754 L+2 → H (79%) 3.51
563 2.2583 0.1009 L→ H-1 (92%)

From the obtained results, it is worth noting that D1-spectrum is strongly influenced by electron transfer
processes. For comparison’s sake to D1, D2 shows a hyper- and bathochromic effect for wavelengths less than
500 nm. The observed bands for D1 (318 and 419 nm) are shifted by + 25 nm for D2. Besides, a lowest intensity
band has been detected at about 563 nm for D2. From optical responses, certainly, the carbonyl (C=O) with
donating group is responsible for the efficient quenching of emission. ICT caused by strongly electron
donating/accepting character interacting substituent is important in governing the optical responses [40-42].
To make easy the interpretation of the optical responses of the dimer compounds under study, the
emission spectra have been fitted by mean of Gaussian peaks for both D1 and D2. As illustrated in Fig. 9, the
PL spectrum of D1 displays two distinct bands noted (1) and (2) for wavelength above 500 nm. However, for
the D2, the emission spectrum shows three optical bands in the same region.

Fig. 9: Fitting Gaussian peaks of emission spectra. The FWHM and A are the full width at half maximum and analytical
integration, respectively.

In addition, a significant emission band in the near infrared domain has detected for D1 (band (3)). In
contrast, relatively lower band was observed at 523 nm (band (4)) for the D2. This letter result can be attributed
4 5 (78)
to excited state ICT. Their corresponding rate of analytic integration is ≈ 17.5%. Accordingly, the
4: (7;)
carbonyl bridging strongly affect the emission response leading to a quenching effect.

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 The optical properties of the compounds based on UV-Vis-NIR and PL spectra together with the high
oscillator strengths are depicted in Fig. 10 for further understanding the optical properties of the dimer
molecules.

Fig. 10: Absorption and emission spectra with oscillator strength (vertical lines) of the investigated compounds.

In order to understand the role played by the carbonyl group as push of electron, we have calculated the
radiative lifetime for both dimers for the sake of comparison. Radiative lifetime (<) define the average time of
the molecule stay at the excited state before emission a photon, which means that lower is the value of < the
more efficient is the emission of the compound. The radiative lifetime can be calculated using the following
expression [43]:
?@
< =>
2(BCDE )8 F
Where C is the velocity of light, BCDE is the fluorescent energy and F is the oscillator strength.
The radiative lifetime values are calculated to be 3.49 ns and 3.51 ns for D1 and D2, respectively.
Surprisingly, the obtained results reveal that compound D1 exhibits a radiative life time relatively lower than
D2, which indicates that D1 has more efficiency in the emission of photons. From energy level diagrams, the
LUMO was evaluated about -2.98 eV and -3.60 eV, for D1 and D2, respectively. The oscillator strength of the
HOMO→LUMO transition is important factor for the efficient ICT, upon photo excitation. In turn, the lower
radiative lifetime is strictly related to this process. A considerable increase in the excited state dipole moment
compared to ground state dipole moment is certainly related substantial redistribution of π-electron densities in
a more polar excited state for the D2 dimer.

3.5. Charge transport and related properties

Designing an efficient multilayer structure requires knowing the precise energy of the hole and electron
transport levels of constituent materials. As mentioned in the introduction part, the reorganization energy could
be an important factor that governs the mobility of charge carriers. Then, as referred to [44], the reorganization
energies for electron (λ" ) and for hole (λ# ) transfer can be defined as:
λ" = BGH − BHH + (BHG − BGG ) (1)
K K G G
(λ# = BG − BK + (BK − BG ) (2)
K H
Where BG BG is the energy of the cation (anion), calculated with the optimized structure of the neutral
molecule and BKK BHH is the energy of the cation (anion), calculated with the optimized cation (anion) structure.
The BKG BHG is the energy of the neutral molecule calculated at the cationic (anionic) state. Whereas, BGG
represent the energy of the neutral molecule at the ground state.
The calculated mobility of charge carriers (λ" and (λ# ) are reported in Table 5. From the obtained
results, we conclude that D2 possesses a high charge transfer ability regarding the large balance of
reorganization energy for hole ((λ# = 0.309) and electron (λ" > = 0.305), unlike D1, where we find that the
reorganization energies values are of 0.311 for hole and 0.503 for electron.

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Table 5: Reorganization energies λ>(eV) for hole (λ# ) and electron (λ" ) transport and other electronic
parameters expressed in eV calculated at B3LYP/6-311g(d,p) level of theory.
Compounds EGK − EK
K G
(EK − EGG ) EGH − EH
H G
(EH − EGG ) λ# λ" IPa EAa η

D1 0.155 0.155 0.182 0.321 0.311 0.503 5.09 3.24 0.925

D2 0.154 0.156 0.156 0.149 0.309 0.305 5.21 3.87 0.670

It is well know that electronic parameters including the adiabatic ionization potential (IPa) and adiabatic
electron affinity (EAa) determination are important task to tune the carriers injection efficiency for OLEDs [45].
The values of IPa and EAa were calculated as described in equations below:
QRS = B T K − B(T G ) (3)

BUS = B T G − B(T H ) (4)

Where B T G , B(T K ) and B(T H ) are the total energies of the neutral, cationic (RC) and anionic forms
of the molecules, respectively. µνλθσδφγηη
Using the above mentioned parameters, we could predict the stability of the compounds through the
VWXHY4X
calculation of their absolute hardness as denoted η and given by: η = (5).
8
The determined energy parameters represent the energy levels relevant to the OLED performance. From
Table 5; we note that both dimer molecules exhibit almost the same values of IPa but distinct values of EAa.
As known, the global hardness η measures the stability of a system in terms of resistance to electron
transfer [46]. In our case, the obtained values are 0.925 eV for D1 and 0.670 eV for D2. This clearly reveals that
the D2 dimer exhibits relatively high stability, implying that the bridging groups has significantly affect the
stability of the CPDT derivatives.

3.6. Organic Light Emitting Diodes (OLEDs) modulation

The analysis of IPa, EAa and reorganization energy shows the high performance of hole and electron
mobility that leads to a high color quality and efficient electroluminescent devices. As illustrated in Fig. 11, the
simulated CIE coordinates were found to be (0.16, 0.04) for D1 and (0.16, 0.09) for D2, corresponding to blue
emission [47]. It resulted in the enhancement of luminescent efficiency.

Fig. 11: The representative CIE color coordinates of D1 and D2.

Multilayer OLEDs can be viewed as two or more layers in order to improve device efficiency. As well
as conductive properties, different materials may be chosen to aid charge injection at electrodes. However, a
common way to balance charge is optimizing the thickness of the charge transporting layers which is hard to
control.

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 As already proposed for the appropriate layers (HIL and EIL with optimal values of the thickness) to
improve the efficiency of carriers injection [25] based on their energy levels diagram (HOMO and LUMO) [48-
50], typical OLED device architecture is depicted in Fig. 12.

Fig. 12: Typical OLEDs architecture including D1 and D2 as emitting layers.

In the three layers based OLED, the insertion of HIL and EIl layers of charge transport materials in
addition to the emitter layer (CPDT derivatives) provides a powerful means to control charge injection, transport
and recombination in OLEDs. It is worth remembering that a large barrier for charge injection results in high
driving voltage, and unipolar charge-transport capability leads to unbalanced charge transport and consequently
low recombination efficiency. In our case, the ultrahigh electron mobility of Alq3 favorites the electron
transport and the deep HOMO level (εHOMO = 5.9 eV) prevents efficiently the hole leakage from the emitting
layer. Further, the small HOMO barrier of NPD (εHOMO = 5.3 eV) allows hole injection to efficiently reach the
emitting layer.
For practical application, we believe that CPDT derivatives with highly planar structures that possess
designed supra-molecular interactions, such as π→π stacking, can greatly enhance the efficiency and stability of
electroluminescence (EL).

3.7. Characteristics current-voltage (I-V)

The electrical responses of the two kinds of devices, simulated using SILVACO software package, were
evaluated based on the current-voltage (I-V) characteristics and results were plotted in Fig. 13. Typical voltages
required to turn OLED devices were closed to 4.6 V for D1 and 7.6 V for D2. It is obviously that the relatively
lower operating voltage was related to the efficient electron injection within device based D1 emitting layer.

Fig. 13: Current-voltage characteristics of devices.

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Conclusion
Two types of π-conjugated CPDT derivatives with small band gaps, were deeply investigated through
theoretical calculations based on the Density Functional Theory (DFT) and its Time-Dependent extension (TD-
DFT) at B3LYP functional with 6-311g(d,p) basis set in acetonitrile. We have demonstrated that a push-pull
effect is certainly expected in these molecules. Especially, the direct comparison between both dimers highlights
the effect of carbonyl (>C=O) bridged groups on emission quenching effect and blue-shifted of the optical
responses due to the photo-induced electron transfer. From optical absorption responses, both dimers exhibit a
relatively narrow band gap (2.38 eV for D1 and 1.91 eV for D2) and low lying energy levels with the HOMO of
-5.36 and -5.51 eV, respectively.
From PL spectra analysis, the studied compounds exhibit an emission in the blue region (419 nm (D1) and
451 nm (D2). The results are supported by CIE coordinates, in which values are determined to be (0.16, 0.04)
for D1 and (0.16, 0.09) for D2 that are strongly located in the blue region.
From the calculated results of reorganization energies, we have demonstrated that compounds exhibit high
performance for charge mobility. Further, current-voltage characteristic has been also simulated. The threshold
voltages are found to be 4.6 V for D1 and 7.6 V for D2. Accordingly, both dimers of molecule have excellent
optical properties and electrical characteristics that make them attractive candidates for designing functional
materials to be used as active layer in OLED devices. Therefore, continuous efforts have been devoted to design
and synthesize high performance deep-blue emitters.

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