Journal of Saudi Chemical Society (2021) 25, 101305

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sa
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ORIGINAL ARTICLE

Efficient tuning of small acceptor chromophores

with A1-p-A2-p-A1 configuration for high efficacy of
organic solar cells via end group manipulation
Muhammad Khalid a,*, Iqra Shafiq a,*, Meiying Zhu b,*, Muhammad Usman Khan c,
Zahid Shafiq d, Javed Iqbal e,f, Mohammed Mujahid Alam g,
Ataualpa Albert Carmo Braga h, Muhammad Imran g

a
Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan
b
Digestive Endoscopic Center, Shanghai Jiao Tong University Affiliated Sixth People’s Hospital, Shanghai, China
c
Department of Chemistry, University of Okara, Okara 56300, Pakistan
d
Institute of Chemical Sciences, Bahauddin Zakariya University, Multan 60800, Pakistan
e
Department of Chemistry, University of Agriculture, 38000 Faisalabad, Pakistan
f
Department of Chemistry, Quaid-i- Azam University, 45320 Islamabad, Pakistan
g
Department of Chemistry, Faculty of Science, King Khalid University, P.O. Box 9004, Abha 61413, Saudi Arabia
h
Departamento de Quı´mica Fundamental, Instituto de Quı´mica, Universidade de São Paulo, Av. Prof. Lineu Prestes, 748, São
Paulo 05508-000, Brazil

Received 21 May 2021; revised 28 June 2021; accepted 3 July 2021

Available online 10 July 2021

KEYWORDS Abstract Now a days, non-fullerene organic compounds are considered with keen interest for the
Non-fullerene acceptor greener energy and potential photovoltaic devices. Herein, novel acceptor chromophores
chromophores; (DPDVD1-DPDVD4) were designed via small acceptor DPDVR compound with A1-p-A2-p-A1
A1-p-A2-p-A1; architecture using promising approach by redistribution of end-capped acceptor moieties. The effect
Organic solar cells; of end-capped acceptor moieties on designed architecture for the photophysical, photovoltaic and
Photovoltaic properties electronic behavior was explored using quantum chemical study. Frontier molecular orbital (FMO)
findings revealed that all the molecules (DPDVD1-DPDVD4) contained narrow band gaps. The
central acceptor moiety (PzDP) was responsible for the transformation of charge in
DPDVD1-DPDVD4. UV–Vis data disclosed that kmax values of DPDVD1-DPDVD4 compounds
were existed in visible region (537.36–517.05 nm). Interestingly, DPDVD2 exhibited the reduced

* Corresponding authors.
E-mail addresses: muhammad.khalid@kfueit.edu.pk, Khalid@iq.usp.
br (M. Khalid), chem19151019@kfueit.edu.pk (I. Shafiq),
meiyingzhu6@yeah.net (M. Zhu).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

https://doi.org/10.1016/j.jscs.2021.101305
1319-6103 Ó 2021 The Authors. Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 M. Khalid et al.

band gap with broader absorption spectra among all chromophores might be due to the negative
inductive effect (
I) of the terminal acceptors. The open circuit voltage (Voc) analysis was per-
formed at the interface between standard donor polymer (PTB7) and DPDVD2. The higher value
(3.34 V) of Voc was observed for DPDVD2 among reference and designed compounds. Further-
more, reorganization energy findings exploited DPDVR-DPDVD4 shown lower values of ke than
kh which indicated that these chromophores were the promising candidates for electron transporta-
tion mobilities. The larger charge mobilities with greater exciton dissociation in excited state for
DPDVD2 were examined, subsequently this compound showed minimum value of ke
(0.015739 eV) among all chromophores. Detailed studies reveal that the entitled molecules can
behave as efficient electron acceptor molecules in organic solar cells (OSCs) that make them inter-
esting candidates for the development of inexpensive optoelectronic devices.
Ó 2021 The Authors. Published by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction small molecule acceptors (NF-SMAs) type materials [14–17]

Currently, energy crises are recognized as major challenge for
mankind because of increased rate of global energy consump-
tion. This energy utilization is increasing with 5.6% rate from
1973 to onward [1]. Many scientists committed to sustain envi-
ronmental power sources to manage this deficiency. Energy
assets: coal, fossil energy, flammable gas and oil power sources
are diminishing, but in addition costly and consumption of the
petroleum products are producing ecological contamination
like CO2 and different risky poisons in our environment.
Energy demand is quickly expanding in terms of economically
rising and industrial point of view. However, it is a significant
issue around the world because of low production of energy
[2]. Power sectors used 23% of sustainable power sources
around the world toward the end of 2011 [3]. Indeed, energy
shortage influenced business, export, daily life and particularly
the industrial zone [4]. In order to prevail the energy deficiency,
production of the electricity from sunlight has been considered
as one of the most promising methodologies. This sophisti-
cated strategy as utilizing solar cells is used to cultivate electric-
ity by solar energy through photoelectric effect. Usually, PV
silicon-based energy devices are found with low cost and high
stability. Photovoltaic (PV) technology has gained rapid devel-
opment because of the growing requirement of sustainable
power sources. The silicon is widely utilized in PV silicon-
based energy gadgets owing to the remarkable proficiency,
everlasting, cost compelling, abundance and eco-friendly nat-
ure [5]. However, recently, it is noticed that silicon has expen-
sive, fragile nature and non-tunable energy levels. While,
organic solar cells (OSCs) consisting of various points of inter-
est such as light weight, simple processability, mechanical flex-
ibility, tunable energy levels, large area of fabrication and
facile synthesis process [6–10]. Further, dye-sensitized solar
cells (DSSCs) have obtained attention due to considerable
photovoltaic performances as their low expenses, great stabil-
ity and tunable visual properties like color and transparency
[11–13]. Furthermore, fullerene acceptors are studied widely
due to their promising photovoltaic performances. However,
with the passage of time, some disbenefits such as expensive
technique, in terms of manufacturing process, non-tunable
capacity of LUMO energy, reduced captivation of sunlight
and poor morphological reliability have been noticed. These
discrepancies make fullerene acceptors as less efficient materi-
als. Therefore, the researchers moved towards non-fullerene
that indicated the best power conversion efficiencies than full-
erene based bulk heterojunction (BHJ) cells [14,18–23].
Researchers found many advantages as effectively tunable
energy levels, economical manufacture, high morphological
consistency and wide optical assimilation over fullerene-
based acceptors. Subsequently, non-fullerene small molecule
acceptors (NF-SMAs) are considered outstanding materials
for tremendously efficient OSCs [24]. Therefore, many
researchers are working now a days on non-fullerene acceptors
A-D-A structure with fine-tuning energy levels, absorption and
charge dispersions [14,25–28] for improving PCEs values.
In view of above advantages of non-fullerene acceptors,
small acceptor chromophore (DPDVR) was selected for quan-
tum chemical designing. In fact, small acceptor chromophore
(DPDVR) with A1-p-A2-p-A1 architecture was synthesized by
Gangala Sivakumar et al. [29] by Heck coupling reaction, in
which dipyrrolo[2,3-b:20,30-e]pyrazine-2,6 (1H,5H)-dione
(PzDP) acts as center building block while 4,5-dicyano-2-
vinylimdazole (vinazene) as end-cap units. The primary photo-
voltaic results specify that DPDVR can be significantly utilized
for creating highly efficient A1-p-A2-p-A1 kind NFAs in OSCs
material. The structural modeling of DPDVR is accomplished
by the end group redistribution keeping same core unit. As lit-
erature survey reveals that the acceptor moieties used to design
different compounds exhibited excellent charge transfer and
photovoltaic properties, so it is expected that these compounds
will shown magnificent solar charge transfer, PCE and photo-
voltaic properties.
For the first time, the derivatives of DPDVR are considered
for photovoltaic study. Herein, we studied maximum absorp-
tion (kmax), energy difference between the orbitals (FMOs),
open-circuit voltage (Voc), density of states (DOS), reorganiza-
tion energies, and transition density matrix (TDM) to check
the influence of various end-capped acceptor units for the
enhancement of the optoelectronic properties of the OSCs.
2. Computational detail
Gaussian 09 package [30] was utilized to execute all the calcu-
lations for title compounds. Initially, Gauss View 5.0 program
[31] was used to construct three dimensional (3D) structures of
the molecules to make input files for Gaussian 09. The struc-
tural optimization of DPDVR was done by using five density
functional theory (DFT) based functionals as B3LYP [32],
Efficient tuning of small acceptor chromophores with A1-p-A2-p-A1 configuration for high efficacy
CAM-B3LYP [33], MPW1PW91 [34], M062X [30] and M06
[35] accompanying with 6–311G(d,p) basis set. After confirma-
tion of structures at true minima potential energy surface using
frequency analysis, time dependent density functional theory
(TDDFT) investigations were accomplished for calculating
the absorption spectra (kmax) of DPDVR at aforesaid levels
and basis set combinations. Among all tested functionals, kmax
result of CAM-B3LYP/6–311G (d,p) functional was found
closer to the experimental reported kmax of DPDVR. There-
fore, CAM-B3LYP/6–311G (d,p) level of theory was chosen
in present study to compute the density of states (DOS), reor-
ganization energies, open-circuit voltage (Voc), transition den-
sity matrix (TDM), frontier molecular orbital (FMO) study
and charge transfer analysis of DPDVR and designed chro-
mophores (DPDVD1-DPDVD4). The CPCM [36] model with
chloroform solvent was utilized for estimating the kmax values
of entitled compounds.
Reorganization energy (RE) of all chromophores was also
investigated at CAM-B3LYP/6–311G (d,p) functional. RE
consisted of two main components i) internal (kint) and ii)
external (kext) reorganization energies. kint explored the quick
changes in internal environment, but external RE deals with
external environmental changes [37,38].Herein, external envi-
ronmental effect was ignored and only internal environmental
effects were considered. So, Eqs. (1) and (2) were used to cal-
culate reorganization energy of electron (ke) and reorganiza-
tion energy of hole (kh), respectively [39].
   0 
ke ¼ E
0
E
þ E

E0 ð1Þ
   0 
kh ¼ Eþ
0
Eþ þ Eþ
E0 ð2Þ
In above mentioned Eqs. (1) and (2), Eþ
and
0 E

0expressed
cationic and anionic energies evaluated from optimal neutral
molecule configurations, respectively. Similarly, E0
andE0þ ,
Fig. 1a Sketch map of DPDVR and various acceptors used for designing of compounds.
3
are the molecular energies of a neutral molecule determined
in anionic and cationic states, respectively. Nevertheless, the
energies of optimized cationic and anionic structures are repre-
sented by E- and E+, respectively while E0 represented single
point energy at ground state [40]. PyMOlyze 2.0 [41], Multiwfn
3.7 [42], Origin 8.0 [43], Avogadro [44] and Chemcraft [45] pro-
grams were used to extract data from output files in terms of
tabular and graphical forms.
3. Results and discussion
A1-p-A2-p-A1 type small acceptor chromophore (DPDVR)
was synthesized by Gangala Sivakumar et al. by Heck cou-
pling reaction [31]. This compound is used as a reference mole-
cule for our quantum chemical investigations. The architecture
of DPDVR is composed of i) dipyrrolo [2,3-b:20,30-e]pyrazine-
2,6 (1H,5H)-dione (PzDP) which acts as center core building
block (A2) ii) 4,5-dicyano-2-vinylimdazole (vinazene) as end-
cap units (A1) and iii) benzene ring which acts as p-bridge that
connected the central core unit (A2) with terminal acceptors
(A1). Since, end-capped modification strategy is successfully
utilized in literature to achieve the excellent photovoltaic
parameters of organic materials [46–49]. Therefore, terminal
acceptor unit (A1) in DPDVR is modified with different effi-
cient terminal acceptor units and new compounds namely
DPDVD1-DPDVD4 are designed. The structures of acceptor
units and these compounds are manifested in Fig. 1(a and b).
The maximum wavelength (kmax) values for DPDVR mole-
cule are analyzed in chloroform solvent at five various func-
tionals as B3LYP, CAM-B3LYP, MPW1PW91, M06 and
M062x in order to select the best functional for investigation.
The maximum absorption (kmax) values of reference molecule
on these levels are observed as 695, 521, 657, 517 and
651 nm, respectively (Table 1). Further, the computed kmax
4 M. Khalid et al.

Fig. 1b Structures of DPDVR and designed compounds (DPDVD1- DPDVD4).

Therefore, all designed compounds are optimized using

Table 1 Comparison of kmax value of reference compound
CAM-B3LYP functional and their optimized geometries are
(DPDV) calculated at different levels of theory with the
obtained at true minima in potential energy surfaces as shown
experimental value in chloroform.
in Fig. S2, while their cartesian co-ordinates are described in
Level of Theory DFT (nm) Exp. (nm) RMSE MAPE Tables S1–S5.
B3LYP 695 547 148 27.05
CAM-B3LYP 521 547 26 4.75
M062X 517 547 30 5.48 4. Frontier molecular orbitals (FMOs) analysis
MPW1 657 547 110 20.11
M06 651 547 104 19.01 Frontier molecular orbital (FMO) study is the best tool for
MO = molecular orbitals, H = HOMO, L = LUMO, characterizing the optical as well as the electronic properties
RMSE = root mean square error, MAPE = mean absolute per- of the molecules [50–52]. Band theory exhibits the noble
centage error essence of HOMO/LUMO by recognizing HOMO as the
valence band and LUMO as the conduction band. It is
believed that depending on the distribution pattern of the
values of DPDVR, as calculated at different functionals are HOMO and LUMO, the charge transfer in photovoltaic OSCs
compared with experimental reported value (547 nm) [31]. It greatly fluctuates. So, FMOs energy difference (DE = ELUMO-
is examined that CAM-B3LYP functional exhibited an appro- EHOMO) is considered a classic parameter [53–57] which pro-
priate agreement with the experimental value (Table 1). More- vides insights about the photovoltaic efficiency in photovoltaic
over, the root mean square error (RMSE) and mean absolute materials. The charge carrier mobility is enhanced in designed
percentage error (MAPE) have also been determined for kmax acceptor molecules (DPDVD1-DPDVD4) through introducing
at different functionals which indicated that CAM-B3LYP is electron withdrawing units, which supported the electronic
more appropriate as reported with smaller error values as delocalization in the molecular systems. Therefore, FMOs
described in Table 1. Subsequently, it is utilized in further cal- study is carried out for acceptor molecules and their results
culations of designed compounds (DPDVD1-DPDVD4) too. are shown in Table 2.
Efficient tuning of small acceptor chromophores with A1-p-A2-p-A1 configuration for high efficacy
Table 2 Energies of frontier molecular orbitals of investigated
compounds.
Compounds EHOMO ELUMO DE
DPDVR
7.38
3.15 4.23
DPDVD1
7.50
3.21 4.29
DPDVD2
6.86
2.83 4.03
DPDVD3
7.29
3.12 4.17
DPDVD4
7.56
3.35 4.21
Egap = ELUMO-EHOMO, units in eV
The calculated EHOMO/ELUMO for DPDVR is obtained to
be
7.38/
3.15 eV with 4.23 eV band gap. Similarly, the
EHOMO are calculated as
7.50,
6.86,
7.29 and
7.56 eV
while the ELUMO energies are obtained to be
3.21,
2.83,

3.12 and
3.35 eV for DPDVD1, DPDVD2, DPDVD3 and
DPDVD4, respectively. AsDE is considered most substantial
tool to represent the charge transfer as well as optoelectronic
properties in molecules. So, the DE values for studied accep-
tors chromophores (DPDVR and DPDVD1- DPDVD4) are
found to be 4.23, 4.29, 4.03, 4.17 and 4.21 eV, respectively.
In an exceptional manner, DPDVD1 contains maximum band
gap among all studied compounds. As maximum Egap value
(4.29 eV) is found in DPDVD1, which have nitro group at
the terminal acceptor unit (1-methyl-4,5-dinitro-1H-imida
zole,2-(3-methyl-4-oxothiazolidin-2-ylidene)malononitrile).
The nitro group with higher electron withdrawing nature (
I),
pulls the electronic cloud towards itself strongly and deacti-
vated the ring by reducing resonance, hence, band gap between
the orbitals can be enhanced. However, the reduction in the
band gap is observed for DPDVD4 (4.21 eV), when nitro
group is replaced with cyano group at A1 (1-methyl-1H-imida
zole-4,5-dicarbonitrile) unit, expressing lower electron with-
drawing effect than nitro group. Moreover, introduction of
carbonyl group in DPDVD4 may be reason of product
enhancements in the resonance process, which lowers the
energy difference between orbitals. Interestingly, this Egap is
further decreased as 4.17 eV in DPDVD3, where sp2 hybridized
sulphur of A1 acceptor (2-(3-methyl-4-oxothiazolidin-2-yli
dene)malononitrile) is mainly responsible which enhanced the
resonance and lower the energy gap of HOMO/LUMO orbi-
tals. Furthermore, the Egap of DPDVD2 is retrieved to be les-
ser than all other molecules, as the presence of chloro group at
terminal acceptor units (4,5-dichloro-1-methyl-1H-imidazole),
signifying positive resonating effect (+R) of chloro group,
hence lower the Egap. It is also examined that all studied accep-
tor chromophores have the lower value of band gaps hence,
can display effective optoelectronic properties (Table 5). Over-
all, the DE values of DPDVR and DPDVD1-DPDVD4 are
found in the following reducing order:
DPDVD1 > DPDVR > DPDVD4 > DPDVD3 > DPDVD2.
Additionally, the contour sides of the FMOs have also been
utilized to explain the electronic cloud transference phenomena
[58], as displayed in Fig. 2. In all studied compounds, the
charge density for HOMO is located all over the chromophore
while LUMO is existed mainly over the central core PzDP unit
(A2) and p-bridge while partially over some atoms of end-
capped acceptors.
5
4.1. Density of states
The density of states (DOS) study was accomplished at CAM-
B3LYP functional with 6-311G (d,p) basis set to elucidate the
outcomes of DPDVR and DPDVD1-DPDVD4, achieved by
FMO study. For the explanation of DOS analysis, we sepa-
rated our compounds into three portions, i.e. Acceptor 1
(end-capped acceptor group), Acceptor 2 (core unit) and p-
bridge (spacer) as shown by blue, green and red lines, respec-
tively and their pictographs are manifested in Fig. 3. The elec-
tronic charge distribution pattern on molecular orbitals could
be changed by utilizing various acceptor units which can be
further justified by calculating percentages of DOS on
HOMO/LUMO. Herein, Acceptor 1 shows electronic distribu-
tion pattern as 30.5, 25.7, 59.9, 37.1 and 36.1% to HOMO
while electronic distribution pattern as 6.7, 7.4, 13.5, 10.11
and 6.7% to LUMO for DPDVR-DPDVD4, respectively. Sim-
ilarly, Acceptor 2 (PzDP) contributes 30.5, 33.8, 20.1, 27.4 and
28.9% to HOMO and 77, 76.3, 78.3, 73.8 and 72.6% to
LUMO in DPDVR-DPDVD4, respectively. Likewise, pi-
linker contributes 39, 40.5, 19.9, 35.5 and 35% to HOMO,
whereas 16.3, 16.3, 8.1, 16.2 and 16.4% to LUMO for
DPDVR-DPDVD4, accordingly. These contributions endorse
that various kind of electronic transitions could be obtained
by modifying terminal acceptors. In DOS pictographs, the neg-
ative values show the HOMO (valence band) while positive
values express LUMO (conduction band) along x–axis and dis-
tance between them represents the band gap [59].The relative
density for HOMO is predominantly found on entire chemical
structure of compounds. However, LUMO is concentrated on
Acceptor 2 (central core PzDP) as well as on p- spacer (ben-
zene) and somehow extent on Acceptor 1. Overall, the charge
distribution patterns illustrated that delocalization of electrons
has been observed and a considerable amount of charge is
moved from the central core portion to the end-capped accep-
tor part via p- spacer in all entitled chromophores
4.2. Optical response
UV–Vis absorption spectra of DPDVR and DPDVD1-
DPDVD4 were investigated in gas phase and chloroform
solvent at CAM-B3LYP/6-311G (d, p) level of theory to
demonstrate the optical properties. The representative transi-
tions are collected in Table 3, while other transitions are
shown in Tables S6–S15 and their spectra are displayed in
Fig. 4. It was examined that extended conjugation along with
powerful electron withdrawing terminal units, exploited a
larger bathochromic shift in UV–Vis absorption spectra
[60]. Our studied compounds with A1-p-A2-p-A1 type having
different end-capped acceptors showing different optoelec-
tronic responses. Higher kmax and low transition energy
values are observed in the all chromophores in chloroform
and gaseous phase.
The calculated values of kmax of all the compounds are
found in the range of 537.36–517.05 nm (chloroform solvent)
and 496.89–519.13 nm (gaseous phase) as can be seen in Tables
S6–S15. The kmax values of the studied compounds in chloro-
form solvent are observed more red-shifted than in gaseous
phase due to the solvent effect. Interestingly, DPDVD2
expressed least value of low transition energy with higher red
shift among all the compounds. This greater absorption
6 M. Khalid et al.

behavior of DPDVD2 may be due to the terminal acceptor unit
(4,5-dichloro-1,2-dimethyl-1H-imidazole) which have chloro
group that exhibited negative inductive effect (
I) as well as
positive resonating effect (+R), which lower the Eg between
orbitals. The decreasing order of kmax of studied compounds
in gas as well as in chloroform is obtained to be
DPDVD2 > DPDVD3 > DPDVD4 > DPDVR > DPDVD1,
which is found in reverse pattern with HOMO-LUMO energy
gap order. According to literature study, molecules having
lower band gap with better absorption properties, subse-
quently such molecules exhibited greater HOMO to LUMO
charge transferability and high-power conversion efficiency
[61]. Above discussion concludes that lower energy gap and
high charge transferability is observed in red shifted com-
pounds leading to high power conversion efficiency and makes
them excellent material to be used in fullerene free based
OSCs.
4.3. Reorganization energy
Reorganization energy (RE) is considered one of fundamental
characteristics for the recognition of the correlation among the
molecular structure along with charge transportation ability of
compounds to design best candidates for the solar cell applica-
tions. The charge transfer capability and RE are inversely pro-
portional to each other. Herein, we calculated the
reorganization energies utilizing the Eqs. (1) and (2) for the
evaluation of charge transportation capability of DPDVR
and DPDVD1-DPDVD4 chromophores and their results are
tabulated in Table 4.

Fig. 2 HOMOs and LUMOs of the DPDVR and DPDVD1-DPDVD4.

Efficient tuning of small acceptor chromophores with A1-p-A2-p-A1 configuration for high efficacy
Fig. 3 Graphical representation of the density of states (DOS) of entitled chromophores.
Fig. 3 (continued)
The anionic and cationic geometries reveal the transforma-
tion of electron and hole towards acceptor from donor part.
Generally, RE can be utilized to compute the transfer of char-
ger density in the D and A moieties. This energy is categorized
7
into two segments: i) kint: and ii)kext: . These segments;kext: and
kint: deal with the polarization influence on the external environ-
ment and the rapid alterations in the internal architecture,
respectively. Usually, researchers consider only thekint: and
neglect the environmental variations. The calculated ke values
for DPDVR and DPDVD1- DPDVD4 are obtained to be
0.015775, 0.017085, 0.015739, 0.017705 and 0.018383 eV,
respectively. Among all the entitled chromophores, the ke
value (0.015739 eV) of DPDVD2 is found less in magnitude
which signifies the higher electrons transfer rate between
HOMO and LUMO. The decreasing order of ke for entitled
chromophores is:
DPDVD4 > DPDVD3 > DPDVD1 > DPDVR > DPDVD2.
Similarly, the calculated reorganization energy values of the
hole for DPDVR and DPDVD1-DPDVD are obtained as
0.016688, 0.017987, 0.019697, 0.017322 and 0.016545 eV,
respectively. The decreasing order of kh for entitled molecules
is:
DPDVD2 > DPDVD1 > DPDVD3 > DPDVR > DPDVD4.
Nevertheless, this analysis revealed that the ke values for enti-
tled chromophores are found lower than kh values except
DPDVD4. This reduction factor in terms of ke values indicates
that all acceptors are inspiring candidates for transfer of
electrons.
8 M. Khalid et al.

Table 3 Computed data of absorption spectra of investigated chromophores in chloroform.

Compounds k (nm) E (eV) f MO contributions
DPDVR 521.29 2.39 2.23 H ? L (91%)
DPDVD1 517.05 2.40 2.18 H ? L (90%)
DPDVD2 537.36 2.31 2.16 H ? L (85%)
DPDVD3 525.33 2.36 2.53 H ? L (88%)
DPDVD4 521.36 2.38 2.57 H ? L (87%)
MO = molecular orbital, f =oscillator strength, H = HOMO, L = LUMO

Fig. 4 Simulated absorption spectra of entitled compounds in (a) chloroform and (b) gaseous phase.

Table 4 Reorganization energy parameters of entitled Table 5 Open circuit voltage and energy driving force of
molecules. entitled compounds.
Compounds ke kh Compounds Voc (V) DE
DPDVR 0.015775 0.016688 DPDVR 3.02 4.23
DPDVD1 0.017085 0.017987 DPDVD1 2.96 4.29
DPDVD2 0.015739 0.019697 DPDVD2 3.34 4.03
DPDVD3 0.017705 0.017322 DPDVD3 3.04 4.17
DPDVD4 0.018383 0.016545 DPDVD4 2.82 4.21
ke :Rate of transfer of electrons; kh :Rate of transfer of hole

Fig. 5 Graphical representation of Voc for entitled chromophores with PTB7.

Efficient tuning of small acceptor chromophores with A1-p-A2-p-A1 configuration for high efficacy 9

Fig. 6 (a) Optimized geometry of DPDVD2:PTB7 (b) Charge transfer between HOMOPTB7 andLUMODPDVD2 .

4.4. Open circuit voltage (Voc) analysis
Open circuit voltage (Voc) plays a crucial role to elucidate the
performance of OSCs, [60,62]. Actually, it explains the highest
amount of current that can be obtained from any optical mate-
rial [63]. Voc can be influenced by various factors such as:
charge carrier recombination, work functions of the electrodes,
external fluorescence proficiency, light source, temperature of
OSCs device, light intensity and many other environmental
factors [64]. Voc is directly related with the energy gap of
HOMO/LUMO of D and A compounds, i.e. DonorHOMO-

AcceptorLUMO. In case of donor PTB7 the simulated value
10
of EHOMO is
6.47 eV. The Voc of PTB7 is variable and
depends on acceptor compound that is associated with it.
Hypothetically the investigated outcomes of Voc of the solar
cells are calculated by Equation (3), reported by Scharber
and his co-workers [65].
M. Khalid et al.
(Figs. 6 and S3]. The effective electronic cloud for LUMO is
concentrated over the DPDVD2 chromophore while HOMO
is located at donor polymer PTB7 in all confirmations [Figs. 6
(b) and S3]. This charge transfer from donor to acceptor pro-
vides solid evidence that all our designed derivatives are effec-
   A  tive acceptor chromophores for OSCs.
Voc ¼ ðED   
HOMO
ELUMO Þ
0:3 ð3Þ
The ELUMO of DPDVR and DPDVD1-DPDVD4 are found
in comparison with EHOMO of donor polymer PTB7 as pre-
sented in Fig. 5 and calculated values of Voc are tabulated in
Table 5.
The Voc values of DPDVR and DPDVD1-DPDVD4 with
respect to the energy difference of HOMOdonor –LUMOacceptor
are obtained to be 3.02, 2.96, 3.34, 3.04 and 2.82 V,
respectively. The Voc of entitled chromophores are
observed to be in following decreasing order:
DPDVD2 > DPDVD3 > DPDVR > DPDVD1 > DPDVD4.
Fantastically, the largest Voc value (3.34 V) is calculated for
DPDVD2 among all the entitled compounds that is found to
be 0.32 V higher than DPDVR. It is quite attractive that
DPDVD2 and DPDVD3 with respect to the HOMOdonor
energy difference reveal greater Voc values of 3.34 and
3.04 V, respectively as compared to DPDVR which illustrated
the greater Voc attributing to their higher LUMO values than
DPDVD1 (2.96 V) and DPDVD4 (2.82 V). Besides this, bind-
ing energy also affects the Voc values of OSC compounds. The
range of binding energy for compounds to exhibit perfect Voc
is 1.2–1.9 eV [66] and our designed acceptor chromophores
have 1.8 eV Eb which demonstrated them as perfect OSC
material.
4.5. Charge transfer analysis
For the understanding the charge transfer (CT) properties in
the studied compounds, the DPDVD2 is selected due to its
low band gap, greater kmax value and considerable electron
mobility associated with low ke value. Complex has been estab-
lished between DPDVD2 and donor polymeric material PTB7
with various conformations in order to explore CT findings
Fig. 7 Transition density matrix of the DPDVR-DPDVD4 at the S1 state.
4.6. Transition density matrix and exciton binding energy
Transition density matrix (TDM) analysis is used to estimate
the nature of transition in DPDVR and DPDVD1-DPDVD4
at CAM-B3LYP/6-311G (d,p) level of theory in gas phase. It
helps to understand the behavior of transitions, mainly from
the ground state (S0) to an excited state (S1) and interaction
between acceptor and donor moieties accompanied by
electron-hole localization [67].The influence of H atoms is
ignored by default due to their minute contribution in transi-
tions. The compounds are divided into three fragments to
explain the TDMx data, i.e. terminal acceptors, p-bridge and
central core acceptor unit represented as A1, p and A2, respec-
tively and their pictographs are shown in Fig. 7.
FMO study disclosed that the charge transfer is signifi-
cantly carried out over the entire compounds which brings
notable changes in TDM heat maps. The TDMx results illus-
trated the simple electronic delocalization on the diagonal of
central core PzDP block (A2) and p and somewhat on terminal
acceptors (A1) in DPDVR and DPDVD1-DPDVD4. These
maps indicate, the charge coherence effectively confined on
PzDP which extended diagonally towards the terminal accep-
tor section via p-bridge as hole electron pair begin to build
diagonally. Additionally, generation of electron hole pair
and excitation of coherence also seem to proliferate non-
diagonally on the entire TDM map.
Furthermore, another parameter binding energy (Eb) is a
significant factor that supports researchers to assess the opto-
electronic properties of OSCs [68]. It enables researchers to cal-
culate the coulombic forces interaction between the hole (h)
and electron (e). The Eb and coulombic interaction of the h
and e are directly proportional with each other and have
Efficient tuning of small acceptor chromophores with A1-p-A2-p-A1 configuration for high efficacy 11

Fig. 7 (continued)

inverse relation with exciton dissociation in the excited state.

Lower Eb leads to higher charge mobilities [69]. Eb of DPDVR Table 6 Computed exciton binding energy (Eb) of entitled
and DPDVD1-DPDVD4 acceptor chromophores is calculated acceptor chromophores.
by utilizing the following Eq. (4) [70]. Compounds EH-L (eV) Eopt (eV) Eb (eV)
Eb ¼ EH
L
Eopt ð4Þ DPDVR 4.23 2.39 1.85
DPDVD1 4.29 2.40 1.89
In Eq. (4), EH
L signifies energy difference between HOMO/ DPDVD2 4.03 2.31 1.72
LUMO. Eopt elucidates the smallest quantity of energy required DPDVD3 4.17 2.36 1.81
for the first excitation from S0 to S1, which produces a pair of DPDVD4 4.22 2.38 1.84
the electron and hole [55,58]. DFT calculated results for Eb of
entitled chromophores are tabulated in Table 6.
The binding energy outcomes designated that all designed
chromophores exhibited lower value of Eb (1.84–1.72 eV) than increases the exciton dissociation by enterprising the break-
DPDVR (1.85 eV) except DPDVD1 compound (1.89 eV). down of coulombic forces between electron and hole. Overall,
These results indicate that all derivatives have the greater abil- the lowest value of Eb is found in DPDVD2 expresses the
ity of exciton dissociation in their excited state. As least Eb maximum charge dissociation potential hence, improves the
12
current charge density (Jsc) and Voc among all the entitled
compounds.
5. Conclusion
In this study, PzDP central core based novel A1-p-A2-p-A1
architecture small non-fullerene acceptors were designed from
DPDVR by end cap modifications for OSCs. The influence of
acceptor moieties on CT and optoelectronic properties was
observed and subsequently found reasonable results for deriva-
tives than their parent molecule. Interestingly, a reduced band
gap was obtained in DPDVD1-DPDVD4 with broader absorp-
tion spectrum than that to their reference. Furthermore, open
circuit voltage investigations revealed that with respect to
HOMOPTB7–LUMOacceptor, all chromophores depicted higher
value of voltage. Reorganization energy findings elucidated
that the entitled compounds are outstanding electron transport
material as have lower ke values. Amazingly, DPDVD2
unveiled the least value of Egap (4.03 eV) with red shifted value
(537.36 nm) as well as lower value (0.015739 eV) of ke mani-
fested higher value of Voc (3.34 V) among entitled compounds
owing to the presence of chloro group at the end capped accep-
tor unit. The lower binding energies were uncovered in
DPDVR and DPDVD1-DPDVD4 which indicated that the
molecules may contain higher power conversion efficiency. It
can be concluded that our computational work provides
worthwhile insights for experimentalists to explore these
attractive OSCs materials for optics and electronics.
CRediT authorship contribution statement
Muhammad Khalid: Conceptualization, Methodology, Project
administration, Investigation, Data curation, Supervision,
Writing - review & editing. Iqra Shafiq: Investigation, Valida-
tion, Visualization, Formal analysis, Writing - original draft.
Mei Ying Zhu: Formal analysis, Writing - review & editing.
Muhammad Usman Khan: Investigation, Validation, Visualiza-
tion, Formal analysis, Writing - review & editing. Zahid Sha-
fiqd: Investigation, Writing - review & editing. Javed Iqbal:
Conceptualization, Data curation, Resources, Supervision,
Investigation, Formal analysis, Writing - review & editing,
Visualization, Validation, Writing - review & editing.
Mohammed Mujahid Alam: Visualization, Validation, Writing
- review & editing. Ataualpa Albert Carmo Braga: Software,
Investigation, Writing - review & editing. Muhammad Imran:
Visualization, Validation, Writing - review & editing.
Acknowledgements
M.M.A and M.I. express appreciation to the Deanship of Sci-
entific Research at King Khalid University Saudi Arabia
through a research groups program under grant number R.
G.P. 1/356/42. A.A.C.B. (grants 2015/01491-3 and
2014/25770-6) is thankful to Fundacão de Amparo à Pesquisa
do Estado de Sao Paulo for financial support. A.A.C.B. (grant
312550/2020-0) also thanks the Brazilian National Research
Council (CNPq) for financial support and fellowships. This
study was financed in part by the Coordenação de Aperfeiçoa-
mento de Pessoal de Nivel Superior do Brasil (CAPES)
Finance Code 001.
M. Khalid et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jscs.2021.101305.
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