Dyes and Pigments 214 (2023) 111236

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Dyes and Pigments

journal homepage: www.elsevier.com/locate/dyepig

Asymmetric perylene-diimide-based polymeric acceptor integrating alkoxy

and alkyl side chains: Synthesis and application for all-polymer solar cell
Junfeng Tong a, *, Zheyu Li a, Yubo Huang a, Yan Wang b, Lichun Zhang a, Lili An c, Pengzhi Guo a,
Chunyan Yang a, Jianfeng Li a, Yangjun Xia a
a
Gansu Province Organic Semiconductor Materials and Technology Research Centre, School of Materials Science and Engineering, Lanzhou Jiaotong University,
Lanzhou, 730070, China
b
Engineering Research Center of Advanced Ferroelectric Functional Materials, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Key
Laboratory of Phytochemistry of Shaanxi Province, Baoji, 721013, China
c
School of Chemical Engineering, Northwest Minzu University, Lanzhou, 730030, China

A R T I C L E I N F O A B S T R A C T

Keywords: Alkoxy side chain embodying the large electronegative oxygen played the critical role in tuning the optoelec­
Perylene diimide tronic and photovoltaic properties. However, few efforts devoted to incorporating the alkoxy side chain into
Alkoxy side chain perylene diimide (PDI) building block. In this contribution, one PDI-containing asymmetric polymeric acceptor
N–O bond
PPDI-HD-OHD-T bearing 2-hexyldecyl (HD) and 2-hexyldecyloxy (OHD) side chains was developed. Also, two
σ-inductive effect
Planarity
symmetric polymeric acceptors PPDI-HD2-T and PPDI-OHD2-T with identical HD and OHD side chains were
Aggregation prepared to systematically study the impact of bonding OHD side chain on light-harvesting and electrochemical
property, molecular configuration, solar cell performance and morphology. Moving from alkyl to alkoxy chains
resulted in at first a red-shifted and then a blue-shifted absorption maximum, gradually downshifted HOMO and
LUMO energy levels, better molecular planarity, enhanced solution and film state aggregation, and improved
photo-stability, these changes resulted from the N–O σ-inductive effect induced by the inserted oxygen, along
with the increased number of alkoxy side chain of PDI ring. Furthermore, PPDI-HD-OHD-T acquired a more
complementary absorption to PTB7-Th, increased electron mobility and benefited morphology. Thereupon, both
improved JSC and FF in PPDI-HD-OHD-T-based device contributed to the boosted PCE of 2.08%, which was
higher than those of symmetric side chains PPDI-HD2-T and PPDI-HD-OHD-T-based devices. To our knowledge,
it is the first attempt to introduce the alkoxy side chain to N-position of PDI to construct asymmetric polymer
acceptor and demonstrated that skillfully tuning the side-chain can effectively affect the electron distribution,
molecular configuration, aggregation, charge mobility, and achieve improved device efficiency in all-polymer
solar cell.

1. Introduction
Recently, all-polymer solar cells (all-PSCs), whose photoactive layer
typically contained both polymeric donors (PDs) and polymeric accep­
tors (PAs), have been strongly investigated, due to the incomparable
advantages over fullerene-based solar cells, including, i) molecular
structural versatility, ii) complementary absorption for harvesting more
sunlight to maximize the short-circuit current density (JSC), iii) readily
tuned electronic energy levels for excellent charge transfer and high
open-circuit voltage (VOC), iv) good flexibility via controlling the vis­
cosity and morphological stability [1‒6]. With the help of development
of PAs and properly selecting PDs, power conversion efficiency (PCE) in
All-PSCs had increased swiftly from 1.90% in POPT:MEH–CN–PPV
system [7] to 8.59% in PTB7-Th:NDP-V system [8], 7.15% PBDB-T:
FPDI-BT1 system [9], 11.76% in PTzBI-Si:N2200 system [10], 9.19%
in PBDB-T:PZ1 system [11] and 16.16% in PBDB-T:PN-Se system [12].
What cannot be neglected is that, such photovoltaic (PV) performance
still lags behind that of A-DA’D-A-structured non-fullerene small mo­
lecular acceptors (NFSMAs)-based solar cells [13‒15].
It has been demonstrated that perylene diimide (PDI) was one unique
building block to construct the efficient electron acceptors, because of
the following appealing advantages, including strong and variable

* Corresponding author.
E-mail address: tongjunfeng139@163.com (J. Tong).

https://doi.org/10.1016/j.dyepig.2023.111236
Received 16 January 2023; Received in revised form 26 February 2023; Accepted 11 March 2023
Available online 13 March 2023
0143-7208/© 2023 Elsevier Ltd. All rights reserved.
J. Tong et al.
sunlight-harvesting ability, good electron affinity resulting from the
strong electron-withdrawing imide group, outstanding electron mobility
due to quasi-planar conjugated molecular structures, and excellent
chemical-, thermal- and photo-stability [16‒22]. For this reason, many
preeminent PDI-based NFSMAs, such as A-D-Aʹ-D-A type hPDI-DTP-IC2F
[23], and A-DA’D-A-type FhPDI-IC2F [24] and PDFC [25], were devel­
oped, and the excellent PCEs ranging from 9% to 12.56% were achieved.
In comparison, the PDI-based polymer acceptors developed slowly.
Inspired by the well-developed designing guidance of polymeric donors,
since the first PA dithienothiophene (DTT)-containing PDI-based
copolymer in 2007 [26], numerous D-A type PDI-based conjugated
PAs, whose backbones was constructed by copolymerizing with vinylene
(V) [8,18], thiophene (T) [27‒29], selenophene (Se) [22,30], tellur­
ophene (Te) [31], bithiophene (2T) [32‒34], thieno[3,2-b]thiophene
(TT) [20,30,35], thienylenevinylene (TVT) [36], benzo[1,2-b:4,5-b′ ]
dithiophene (BDT) [35], [37‒39], naphtho[1,2-b:5,6-b’]dithiophene
(NDT) [35], cyclopenta[1,2-b: 5,4-b′ ]dithiophene (CPDT) [4], dithieno
[3,2-b:2′ ,3′ -d]pyrrole (DTP) [40] and so on, have been developed.
Amongst these PDI-based PAs, only limited ones such as PPDIODT [29],
PDI-V [30] and NDP-V [8] exhibited excellent PCE of over 6%.
In addition to regulating the polymer backbone, side chains
including alkyl (R), alkoxy (RO), alkylthio (RS), alkylthienyl (RT) etc.
played a momentous role in adjusting the solubility, absorption, elec­
tronic energy level, crystallinity, aggregation and PV performance [41‒
47]. For example, Janssen et al. shortened the branched side chain from
2-decyltetradecyl (DT) to 2-octyldodecyl (OD) then to 2-hexyldecyl
(HD) in diketopyrrolopyrrole (DPP)-based conjugated polymers (CPs)
in 2014, and found HD-PDPPTPT bearing the shortest HD chain
exhibited narrow fibrils and acquired the highest PCE of 7.4% [48].
Following, a series CPs with the backbone of 4,8-dialkoxy- or 4,8-dia­
lkylthienylbenzo[1,2-b:4,5-b′ ]dithiophene (BDT or BDTT)-alt-6-al­
kyl-TT- thieno[3,4-c]pyrrole-4,6(5H)-dione (ttTPD) were developed,
and octyl chain on TT-bridge in PBDTT-8ttTPD:PC71BM system exhibi­
ted the highest molecular planarity, molecular stacking and balanced
charge mobilities, resulting in high PCE up to 8.67% [49]. Different side
chains were introduced into dialkylthienyl substituted BDT-alt-benzo[1,
2-c:4,5-c′ ]dithiophene-4,8-dione (BDD)-based CPs, and the steric hin­
drance was caused by the longest HD chain and thus PBT1-EH bearing
moderate bulky side chain on BDD unit acquired the excellent PCE over
10% both in PC71BM and ITIC-Th systems [43]. After side chain linked
to conjugated thiophene π-bridge in naphtho[1,2-c:5,6-c′ ]bis [1,2,5]
thiadiazole (NT)-alt-TT-containing CPs reduced from DT to OD, an ex­
pected face-on molecular orientation and 3.41-fold enhanced PCE of
10.33% in NT812:PC71BM blend film was observed [50]. When the side
chain extended from HD to OD in TT-flanked BDT-alt-bisalkylthienyl-NT
(DTNT)-based CPs, the PCE was increased from 3.99% to 5.21% because
an enhanced solid molecular stacking in OD-chain-containing polymer
led to increased and balanced charge mobility [51]. In 2019, Wei and his
coworkers developed two alkyloxy-substituted benzo[c][1,2,5]oxadia­
zole (BO)-based CPs BO2FC8 and BO2FEH, and found that linear n-octyl
side chain facilitated the stacking and induced the acceptor m-ITI­
C-OR-4Cl to produce the benefited aggregation which could support
larger interfacial area and more charge transfer and transport pathways,
contributing to 71.88% increased PCE from 6.4% to 11.0% [52].
Recently, Wang et al. introduced the hybrid chain (containing cyclic and
alkyl chains) and modified the star donor D18 to develop series of CPs.
The controlled aggregation enabled the desired exciton dissociation,
reduced charge recombination as well as balanced charge transport,
resulting in the prominent PCE of 18.20% in D18-C6Ch-based device
when paring with L8-BO [53].
In comparison with the above great variety of PDs, relatively few
attentions on alkyl side chain optimization for naphthalene diimide
(NDI)- and PDI-based polymer acceptors have been received [32,44,46,
54,55]. Different branched side chains (HD, OD and DT) were bonded
into the N-position of NDI-alt-thiophene backbone, PNDIT-HD bearing
the shortest HD chain not only adopted the face-on crystalline
2
Dyes and Pigments 214 (2023) 111236
orientation but also obtained the optimized morphology with finely
separated phased domains, which led to enhanced and balanced charge
mobilities and thus elevated PCE approaching 6% [54]. Meanwhile, Jen
et al. replaced the 2,2′ -bithiophene (T2) in N2200 with 3,3′ -difluoro-2,
2′ -bithiophene (FT2) to obtain fluorinated CPs, and P(NDI2DT-FT2)
with DT side chain possessing the favorable morphology exhibited the
improved exciton dissociation and charge carrier transport, contributing
to an increased PCE of 6.71% [55]. Subsequently, Kim et al. optimized
the side chain of N2200 and found P(NDI2HD-T2) possessing the
shortest chain emerged the most closed packing, resulting in the optimal
field-effect transistor (FET) mobility up to 1.90 cm2 V− 1 s− 1 and best
PCE of 6.11% [44]. As for PDI-based CPs, Zhao and her coworkers sys­
tematically investigated the effect of the dove-tailed type side chain
length (PDI-V-x) from PDI-alt-vinylene backbone in 2017, and limited
impact on energy level and absorption but the increased out-of-plane
(OOP) lamellar spacing were found with the increase of branched side
chain. Therefore, PTB7-Th:PDI-V-C7-based device afforded the best PCE
of 7.44% [46]. Recently, Chen et al. synthesized a
semi-perfluoroalkyl-containing PDI-based PA P(4CF8CH-PDI-TT),
which exhibited an 8.9% increased PCE of 3.43% than that of regular
alkyl chain-containing P(20CH-PDI-TT) in the pseudo-planar hetero­
junction all-PSCs when pairing with PffBT4T-2OD [32]. Obviously, the
effect of flexible side chain in the PDI-based polymer acceptors on the
optoelectronic property and photovoltaic performance was still unclear.
In comparison with alkyl, alkoxy side chains which comprised the
large electronegative oxygen not only affected the molecular weight,
solution processability, miscibility, but also tuned the absorption, en­
ergy level, dipole moment and planarity, aggregation and intra­
molecular charge transfer (ICT) effect as a result of electron-donating
and conformational locking effect because oxygen atoms possessed the
σ-inductive effect and π-conjugative effect [56‒61]. In 2014, Woo and
his coworkers incorporated HD chain into benzene to prepare a class of
benzothiadiazole (BT)-based CPs, and found that bisfluoro-BT
PPDT2FBT-based device afforded the winning PCE 7.06% due to an
improved molecular planarity [56]. Following, 3-alkyloxy-3′ -2,2′ -bi-
thiophene (TRTOR)-difluorinated BT copolymer exhibited high molec­
ular planarity, mobility and enhanced PCE of 9.76% [57]. As for NFAs,
when different alkoxy side chain (CH3O‒, C6H13O‒ and C10H21O‒) was
introduced to the central benzene of IDIC-2F, the red-shifted absorption
and raised ELUMO along with the increase of alkoxy chains, and the best
PCE of 13.01% in longest PM6:DO-IDIC-2F-based device were obtained
[62]. Besides, the alkoxy approach was also applied in other NFAs-based
systems, including PM6:Y6–O (16.6%) [58], PM6:Y6–1O (17.6%) [59],
PM6:BZ4F–O-3 (14.69%) [60], PM6:Y6–O2BO (16.2%) [63], PM6:
BTPO-NF (17.11%) [64] etc. However, few attentions have been paid
to incorporate the alkoxy side chain into the PDI-based PAs and probe
into the effect on molecular configuration, physicochemical properties
and PV performance.
Considering the importance of flexible alkyl and alkoxy side chains,
three donor-acceptor PAs, PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-
OHD2-T (Scheme 2), in which different side chains 2-hexyldecyl (HD)
and 2-hexyldecloxy (OHD) were bonded into the N-position of PDI ring,
were synthesized to figure out the influence of alkoxy side chain on the
absorption, energy level, molecular configuration, molecular electro­
static optional (ESP), aggregation, mobility, morphology and PV per­
formance. It was clear that with the increase of alkyloxy side chain
number, first red-shifted then blue-shifted maximum absorption peak,
first increased then decreased optical bandgap, both gradually down-
shifted EHOMO and ELUMO, enhanced planarity and aggregation as well
as improved photo-stability were achieved. Furthermore, PPDI-HD-
OHD-T bearing both HD and OHD chains acquired the more comple­
mentary absorption with PTB7-Th, enhanced electron mobility and
desired morphology, resulting in a boosted PCE of 2.08% than those
(1.78% and 1.24%) of symmetric side chain-containing PPDI-HD2-T-
and PPDI-OHD2-T-based devices. As far as we know, this was the first
time to introduce the alkyloxy side chain into N-position of PDI ring
J. Tong et al.
aimed at constructing polymeric acceptor and probe into the impact of
N–O bond on optical-electrical characteristic and device performance.
2. Results and discussion
2.1. Synthesis and characterization
The new oxygen-containing aliphatic amine 2-hexyldecyloxyamine
(NH2-OHD) was prepared according to modified procedure [65,66] in
light of classical Gabriel reaction and obtained as colorless oil with the
total yield of 33.6%. Synthetic route for dibromide PDI-HD-OHDBr2
involving HD and OHD side chains was exhibited in Scheme 1, and the
corresponding details were listed in the later experimental section.
Aminolysis reaction between 1,7-dibromo-3,4,9,10-perylenetetracar­
boxylic dianhydride (PTCDABr2) and 2-hexyldecylamine (H2N-HD)
[67] utilizing nBuOH and H2O (1:1) as solvent gave the symmetric
PDI-HD2Br2 [26], subsequently treated with KOH in tBuOH to form
partially hydrolyzed PDI-HDBr2, finally PDI-HDBr2 reacted with
NH2-OHD to obtain PDI-HD-OHDBr2. Meanwhile, the other symmetric
PDI-OHD2Br2 was obtained via similar aminolysis reaction between
PTCDABr2 and NH2-OHD with the yield of 57%. Structures of these key
intermediates and dibromides were characterized by 1H NMR, 13C NMR
(Fig. S1~S9) and elemental analyses. Note that, three dibromides
PDI-HD2Br2, PDI-HD-OHDBr2 and PDI-OHD2Br2 all exhibited 1,7- and
Scheme 1. Synthesis of dibromides PDI-HD2Br2, PDI-HD-OHDBr2 and PDI-OHD2Br2.
3
Dyes and Pigments 214 (2023) 111236
1,6- isomers, and the corresponding 1H NMR spectra (Fig. S3, S6 and S8)
exhibited that the mole ratio (1,7-/1,6-) was about 4:1, which was
similar with the Hou’s observation [29].
As exhibited in Scheme 2, three studied polymeric acceptors PPDI-
HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T were synthesized via Stille
coupling between thiophene-based bistin comonomer (TSn) [66] and
corresponding dibromides with the yields of 76%, 74% and 71%,
respectively (Table S1) [67]. We can see that, during these 1H NMR
spectra (Fig. S10~S12), the signals ranging from 8.80 to 7.40 ppm were
attributed to aromatic hydrogen from PDI ring, one spanning from 7.40
to 7.00 ppm belonged to aromatic hydrogen from thiophene ring, ones
around 4.15, 1.90, 1.60–1.20 and 0.88 ppm were ascribed to aliphatic
hydrogen, which suggested these resulted polymer acceptors were suc­
cessfully synthesized. Moreover, these polymers exhibited excellent
solubility in chloroform (CF) and chlorobenzene (CB). Finally,
number-average molecular weight (Mn) and polydisperse index were
15.7 kDa and 1.85 for PPDI-HD2-T, 13.8 kDa and 1.98 for PPDI-H­
D-OHD-T and 14.3 kDa and 2.04 for PPDI-OHD2-T, respectively.
2.2. Optical property, aggregation behavior and photo-stability
To clarify the impact of introducing OHD side chains on the ab­
sorption, UV–Vis absorption spectra of PPDI-HD2-T, PPDI-HD-OHD-T
and PPDI-OHD2-T in CB and thin-film state were measured and
J. Tong et al.
Scheme 2. Synthesis of the polymeric acceptors PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T.
exhibited in Fig. 1 and Table 1. Three polymeric acceptors exhibited
broad absorption ranging from 300 to 800 nm, which was consistent
with PDI-alt-thiophene polymer backbone [27,29], exhibiting comple­
mentary absorption with the selected donor PTB7-Th. PPDI-HD2-T and
PPDI-HD-OHD-T showed the similar absorption profile, and broad and
relatively weaker peak around 555 nm were ascribed to π-π* transition
from PDI unit. In contrast, PPDI-HD-OHD-T showed the three distinc­
tive absorption peaks, and peak at 343, 496 and 571 nm were in turn
ascribed to π-π* transitions of thiophene and PDI units as well as one
571 nm was belonged to thiophene-to-PDI charge transfer, which similar
with those of P(4CF8CH-PDI-TT), P(20CH-PDI-TT) [32] and PPDI-TT2F
[34]. PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T exhibited the
maximum absorption peak (λmax) at 569, 557 and 571 nm with the
molar absorption coefficients (ε) of 1.67 × 104, 1.46 × 104 and 1.54 ×
104 L mol− 1 cm− 1 (Fig. S13 and Table S1), indicating 8 nm blue-shifted
value and 4 nm red-shifted value as well as a first decreased then
increased ε when introducing OHD side chain. For clarity, ε of PTB7-Th
was found to be 9.03 × 104 L mol− 1 cm− 1 (Fig. S14). Compared with
solution, the λmax peak in film state all blue-shifted, and the blue-shifted
values of 34 nm for PPDI-HD2-T, 3 nm for PPDI-HD-OHD-T and 66 nm
for PPDI-OHD2-T were found. Furthermore, the onset absorption edges
(λonset) of PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T were in
turn 745, 715 and 765 nm, corresponding to the optical band gap (Eopt
of 1.66, 1.75 and 1.62 eV, respectively (Table 1). As exhibited in
Fig. S15, PTB7-Th:PPDI-HD-OHD-T-based blend film exhibited slightly
wider and higher light-harvesting capability between 500 and 800 nm.
To understand the influence of introducing OHD side chain of these
PDI-based polymer acceptors on the aggregation in solution state,
temperature-dependent absorption (TD-Abs) spectra of PPDI-HD2-T,
PPDI-HD-OHD-T and PPDI-OHD2-T were measured in Fig. S16. We can
see that, when the temperature increased from 25 ◦ C to 105 ◦ C, the
maximum absorption peak was all blue-shifted and the intensity
decreased. It was known that as the temperature elevated, the interchain
Fig. 1. Absorption of polymeric acceptors PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T in solution (a) and thin film (b).
Dyes and Pigments 214 (2023) 111236
torsion in the polymer backbone increased, resulting in a decreased the
interchain aggregation and a weaken and/or broken conjugation sys­
tem, thus the absorption spectrum was blue-shifted [68,69]. In detail,
the blue-shifted maximum peak values of 9 nm from 569 to 560 nm, 6
nm from 557 to 551 nm, and 10 nm from 571 to 561 nm, and decreased
absorption intensity values of 5.75% from 0.7536 to 0.7103, 4.55% from
0.7669 to 0.7320, 5.96% from 0.7252 to 0.6820 were observed for
PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T, respectively, these
small changes indicated that these studied polymer acceptors showed
the commensurate solution aggregation (Fig. S16d). Furthermore, the
aggregation property in the solid thin film was also investigated by X-ray
diffraction test, as shown in Fig. S17. Diffraction peak around small
angle region was found in PPDI-HD-OHD-T pure film, 2θ = 3.77◦ ,
corresponding to the distance separated by flexible HD and/or OHD side
chains attached into N-position of PDI of 23.41 Å. In contrast, broad
diffraction peak placed at large angle scope were found to be 2θ =
22.84◦ , 23.10◦ and 23.14◦ , corresponding to the distances separated by
polymer backbone of 3.89 Å, 3.85 Å and 3.84 Å for PPDI-HD2-T,
PPDI-HD-OHD-T, and PPDI-OHD2-T, respectively (Table S2). Defi­
nitely, the observed enhanced π-π stacking interaction and ordered
molecular structure in PPDI-HD-OHD-T combing alkyl and alkoxy
chains was prone to obtain high carrier mobility and thus improved PV
g ) performance in theory.
The absorption versus light-soaking time was measured in order to
assess the photostability difference for these studied PDI-containing
polymer acceptors which had different flexible chains, as illustrated in
Fig. S18. It was exhibited that, along the light-soaking time lengthened,
the maximum absorption peak blue-shifted and the absorption intensity
weakened. After undergoing 240 min light-soaking, the blue-shifted
values of 12, 9 and 6 nm and decreased intensity value of 9.59%,
5.36% and 3.53% were observed for PPDI-HD2-T, PPDI-HD-OHD-T and
PPDI-OHD2-T, respectively. Obviously, introducing alkoxy side chain
was helpful in enhancing the photostability and thus was good for
4
J. Tong et al. Dyes and Pigments 214 (2023) 111236

Table 1
Optical and electrochemical data for PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T.
Polymer Acceptor Solution Film Eopt
g
a
(eV) φonset
ox (V) red (V)
φonset EHOMOb (eV) ELUMOc (eV) Eec
g
d
(eV)

λmax (nm) λmax (nm) λsh (nm) λonset (nm)

PPDI-HD2-T 569 320,535 – 745 1.66 1.16 − 0.82 − 5.86 − 3.88 1.98
PPDI-HD-OHD-T 557 325,554 – 715 1.75 1.18 − 0.81 − 5.88 − 3.89 1.99
PPDI-OHD2-T 343,496,571 330,505 – 765 1.62 1.21 − 0.76 − 5.91 − 3.94 1.97
PTB7-Th 321,636,705 698 636 761 1.63 0.53 − 1.13 − 5.23 − 3.57 1.66
a
Estimated from absorption onset of polymeric acceptors in the film (Egopt = 1240/ λfilm
onset ).
b
Calculated from oxidation potential for polymeric acceptors (EHOMO = –e(φonset
ox + 4.70) (eV)).
c
Calculated from reduction potential for polymeric acceptors (ELUMO = –e(φonset
red + 4.70) (eV)).
d
Calculated from Egec = –(EHOMO – ELUMO) (eV).

practical application [70,71].
2.3. Electrochemical properties
To probe into the influence of introducing OHD side chain on elec­
tronic energy level, the cyclic voltammetry (CV) behavior were
measured to evaluate the EHOMO and ELUMO, as exhibited in Fig. 2. We
can find that, the oxidation onset potential (φonset
ox ) and reduction onset
peak (φonset
red ), were found to be 1.16 V and − 0.82 V for PPDI-HD2-T, 1.18
V and − 0.81 V for PPDI-HD-OHD-T, and 1.21 V and − 0.76 V for PPDI-
OHD2-T, respectively. Note that the Fc/Fc+ redox couple (φ1/2) was
found to be 0.10 V against Ag/AgNO3 reference electrode and the
oxidation potential of ferrocene was − 4.80 [71]. On the basis of the
polymeric acceptors on molecular geometries and electronic proper­
ties, density functional theory (DFT) analysis at B3LYP-D3(BJ)/6-31G
(d) level (Gaussian09) was performed [74]. For achieving the simplifi­
cation, the polymer backbones of PPDI-HD2-T, PPDI-HD-OHD-T and
PPDI-OHD2-T were substituted by two repeating units and the flexible
side chains 2-hexyldecyl and 2-hexyldecyloxy were simplified into
iso-butyl and iso-butyloxy, respectively, and thus these studied polymer
acceptors were denoted as (PDI-B2-T)2, (PDI-B-OB-T)2 and
(PDI-OB2-T)2, respectively.
As shown in Fig. 3, the HOMO orbits were predominantly distributed
over the whole polymer backbone, whilst the LUMO orbitals mainly
distributed on the PDI ring. The calculated EHOMO, ELUMO, and band-gap
Eca
g values were in turn found to be − 5.73, − 3.54, and 2.19 eV for (PDI-

formulae EHOMO = –e(φonset – (φFc/Fc ‒ 4.80)), ELUMO = –e(φonset

+ B2-T)2, − 5.80, − 3.59 and 2.21 eV for (PDI-B-OB-T)2, and − 5.86, − 3.65
red –
and 2.21 eV for (PDI-OB2-T)2. The gradually decreased variation trend
ox
(φFc/Fc ‒ 4.80)) and the electrochemical bandgap (Eec g ) = –(EHOMO –
+

ELUMO) [72], EHOMO/ELUMO/ Eec were − 5.86/‒3.88/1.98 eV, − 5.88/‒
g tests along with the increase in number of alkyloxy side chains.
3.91/1.99 eV, and − 5.91/‒3.94/1.97 eV, respectively. For better
illustrating the energy level variation, the energy level bar chart for
these PDI-based polymer acceptors and donor PTB7-Th was made in
Fig. 2b. After introducing alkyloxy flexible side chain into polymeric
backbone, the EHOMO was decreased from − 5.86 eV to − 5.88 eV then to
− 5.96 eV, meanwhile, the ELUMO decreased from − 3.88 eV to − 3.91 eV
then to − 3.94 eV, which could be explained by an enhanced the
electron-withdrawing ability resulted from the σ-inductive effect due to
introducing the large electronegative oxygen atom into N-position of
diimide. The observed 0.03 eV down-shifted ELUMO would damage the
VOC of corresponding All-PSCs. We also noted that the ELUMO difference
of 0.31–0.37 eV between PTB7-Th and these PDI-based polymer ac­
ceptors could guarantee efficient driving force for exciton dissociation
[68,73].
2.4. DFT calculations
To unravel the impact of introducing OHD side chains of PDI-based
of EHOMO and ELUMO agreed with that of energy levels measured from CV
Furthermore, the dihedral angles θ1, θ2 and θ3 between thiophene
linkage and PDI ring were observed to be − 121.72o, 131.24o and
124.23o for (PDI-B2-T)2, 127.71o, − 127.66o and − 131.25o for (PDI-B-
OB-T)2, and 127.72o, − 127.57o and − 131.98o for (PDI-OB2-T)2,
respectively (Table 2). Interestingly, dihedral angle between two PDI
rings during these model molecules was calculated to be 23.26o for (PDI-
B2-T)2, 20.13o for (PDI-B-OB-T)2 and 19.08o for (PDI-OB2-T)2,
respectively (Fig. 3). Obviously, after incorporating alkyloxy side chain
into polymer backbone, the improved molecular planarity tallied with
the result from XRD measurement, which was prone to acquiring the
elevated charge mobility.
Molecular surface ESP of model compounds (PDI-B2-T)2, (PDI-B-OB-
T)2 and (PDI-OB2-T)2 was also calculated and shown in Fig. 4 and
Table S3. Seen from Fig. 4a, most surfaces of these studied model
compounds had the positive ESP value, while, the negative ESP mainly
distributed over the diimide group. After incorporating alkyloxy side
chains into polymer backbone, the ESP distribution scope become wider

Fig. 2. CV plots (a) and energy level diagram (b) for PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T.

5
J. Tong et al.
Fig. 3. Optimal molecular geometries and molecular orbital distribution for model molecules (PDI-B2-T)2, (PDI-B-OB-T)2 and (PDI-OB2-T)2.
(from − 36.82 to 30.92 kcal mol− l for (PDI-B-OB-T)2, from − 37.79 to
29.93 kcal mol− l for (PDI-OB-T)2, from − 32.30 to 29.62 kcal mol− l for
(PDI-B-T)2) (Fig. 4b and Table S3). We also found that the values for
overall surface area and molecular polarity index (MPI) (the larger MPI
means higher overall molecular polarity) were both increased along
with the increase of alkyloxy side chain, and (PDI-B-OB-T)2 had the
largest overall surface area of 1129.82 Å2 and largest MPI value of 10.21
kcal mol− 1 (Table S3). The increased MPI values of (PDI-B-OB-T)2
bearing alkyloxy side chain was helpful in facilitating exciton dissocia­
tion and accelerating charge transfer [67,70].
2.5. Photovoltaic properties
To understand the influence of incorporating alkoxy side chain on
the PV behaviour, devices with the structure ITO/PEDOT:PSS/PTB7-Th:
polymeric acceptors/PDINO/Al were fabricated. The device testing
procedure included selecting the donor:acceptor (D:A) weight ratio and
applying 1,8-diiodiooctane (DIO) solvent additive, as exhibited in
Fig. S19 and Table S4. Note that the solution concentration of these
polymeric acceptors was controlled to 10 mg mL− 1 in the CB processing
solvent. The D:A weight ratios were 1:1.2, 1:1 and 1.2:1 for PTB7-Th:
PPDI-HD2-T, 1:1.5, 1:1.2, 1:1 and 1.2:1 for PTB7-Th:PPDI-HD-OHD-T,
and 1:1.2, 1:1 and 1.2:1 for PTB7-Th:PPDI-OHD2-T, respectively. And
6
Dyes and Pigments 214 (2023) 111236
the best weight ratio of PTB7-Th:PPDI-HD2-T, PTB7-Th:PPDI-HD-OHD-
T and PTB7-Th:PPDI-OHD2-T in was 1:1, 1:1.2 and 1:1. Under the each
best D:A weight ratio, PPDI-HD2-T-based device got the PCE of 1.25%,
with the VOC of 0.73 V, the JSC of 5.13 mA cm− 2, FF of 33.42%, PPDI-
HD-OHD-T-based device acquired the PCE of 1.10%, with the VOC of
0.58 V, the JSC of 4.97 mA cm− 2, FF of 38.20%, and PPDI-OHD2-T-based
device obtained the PCE of 0.88%, with the VOC of 0.58 V, the JSC of
4.58 mA cm− 2, the FF of 32.99%. Following, since the solvent additive
can tune the morphology and enlarge the PV performance [68,73,75],
we further applied the high boiling point DIO to enhance the perfor­
mance. We can find that 2.74% increased VOC from 0.73 to 0.75 V,
17.74% elevated JSC from 5.13 to 6.04 mA cm− 2, 17.32% enhanced FF
from 33.42% to 39.21% assisted by maximized shunt resistance (RSH)
from 273.33 to 322.27 Ω cm− 2 and minimized series resistance (RS) from
47.14 to 27.32 Ω cm− 2 in PTB7-Th:PPDI-HD2-T-based device, resulted
in an improved PCE from 1.25% to 1.78%. As for PTB7-Th:PPDI-H­
D-OHD-T-based device, 8.62% increased VOC from 0.58 to 0.63, 42.05%
elevated JSC from 4.97 to 7.06 Ω cm− 2, 21.88% enhanced FF from
38.20% to 46.56% assisted by increased RSH from 179.26 to 468.49 Ω
cm− 2 and decreased RS from 30.05 to 18.51 Ω cm− 2, led to an improved
PCE from 1.10% to 2.08%. While, in the PTB7-Th:PPDI-OHD2-T-based
device, 12.07% increased VOC from 0.58 to 0.65, 6.77% elevated JSC
from 4.58 to 4.89 Ω cm− 2, 18.82% enhanced FF from 32.99% to 39.20%
J. Tong et al. Dyes and Pigments 214 (2023) 111236

Table 2 cm− 2 and the 18.75% improved FF of 46.56% regardless of the 16%
Dihedral angles for (PDI-B2-T)2, (PDI-B-OB-T)2 and (PDI-OB2-T)2. decreased VOC of 0.63 V. However, incorporating two OHD side chains
Model molecule Structure Dihedral angle (deg) into the polymer backbone, PTB7-Th:PPDI-OHD2-T-based device ob­
tained the 40.38% decreased PCE of 1.24%, with 30.74% down-shifted
(PDI-B2-T)2 θ1 = − 121.72,
θ2 = 131.24, JSC of 4.89 mA cm− 2 and 15.81% decreased FF of 39.20% even in the
θ3 = 124.23. 3.17% boosted VOC of 0.65 V. Furthermore, the corresponding EQE
profiles were similar with the preceding absorption spectra (Fig. 1b),
and the improved EQE response ranging from 480 to 750 nm in PTB7-
Th:PPDI-OHD2-T correlated with red-shifted and broaden absorption.
(PDI-B-OB-T)2 θ1 = 127.71,
We also noted that the integrated current density obtaining from EQE
θ2 = − 127.66, curves were 5.95 mA cm− 2 for PPDI-HD2-T, 6.98 mA cm− 2 for PPDI-
θ3 = − 131.25. HD-OHD-T and 4.80 mA cm− 2 for PPDI-OHD2-T, respectively, these
deviations (smaller than 5%) indicated that the JSC values were credible.
Evidently, the increase in PTB7-Th:PPDI-HD-OHD-T-based device
ranging from 500 to 700 nm can account for the boosted JSC compared
with those of PPDI-HD2-T- and PPDI-OHD2-T-based devices.
(PDI-OB2-T)2 θ1 = 127.72,
θ2 = − 127.57,
θ3 = − 131.98. 2.6. Charge mobility

To clarify PPDI-HD-OHD-T-based device bearing one OHD side

assisted by increased RSH from 193.39 to 324.40 Ω cm− 2 and decreased
RS from 40.79 to 36.07 Ω cm− 2, resulted in an improved PCE from 0.88%
to 1.24% (Table S4). As expected, DIO played the positive effect in
boosting the PV performance.
Going through screening out the different D:A weight ratio and uti­
lizing solvent additive, the optimized J-V plot and external quantum
efficiency (EQE) curve were listed in Fig. 5. PTB7-Th:PPDI-HD2-T-based
device acquired the PCE of 1.78%, with the VOC of 0.75 V, JSC of 6.04
mA cm− 2 and FF of 39.21%. Incorporating one OHD side chain into
polymer backbone, PTB7-Th:PPDI-HD-OHD-T-based device showed the
16.85% increased PCE of 2.08%, with 16.89% enhanced JSC of 7.06 mA
chain acquired the elevated FF and PCE, electron transfer characteristic
was measured utilizing the space-charge-limited-current (SCLC) method
[76,77]. The electron mobility (μe) was measured and collected in Fig. 6.
Note that the thickness for these studied active layers were approxi­
mately 90 nm for PTB7-Th:PPDI-HD2-T-, 95 nm for PTB7-Th:PPDI-H­
D-OHD-T- and 90 nm for PTB7-Th:PPDI-OHD2-T-based blend films,
respectively (Table S5). Therefore, the μe values were found to be 8.32
× 10− 6, 2.25 × 10− 5 and 7.22 × 10− 6 cm2 V− 1 s− 1 for PTB7-Th:
PPDI-HD2-T-, PTB7-Th:PPDI-HD-OHD-T-, and PTB7-Th:
PPDI-OHD2-T-based devices, respectively (Table 3). Obviously,
1.70-fold and 2.12-fold increased electron mobility of PPDI-H­
D-OHD-T-based device than those of symmetric PPDI-HD2-T- and
PPDI-OHD2-T-based devices correlated with improved molecular
planarity obtained from DFT predication and enhanced molecular
stacking interaction found in XRD analysis, and could partially account

Fig. 4. ESP distribution (a) and ESP area distribution (b) of (PDI-B2-T)2, (PDI-B-OB-T)2 and (PDI-OB2-T)2.

Fig. 5. Optimized J-V (a) and EQE (b) curves of PPDI-HD2-T-, PPDI-HD-OHD-T- and PPDI-OHD2-T-based devices with 3% DIO.

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J. Tong et al. Dyes and Pigments 214 (2023) 111236

Fig. 6. J-V (a) and J0.5-V (b) curves of electron-only devices based on PTB7-Th:PPDI-HD2-T, PTB7-Th:PPDI-HD-OHD-T and PTB7-Th:PPDI-OHD2-T.

acceptors. The χ values were found to be 0.0116K, 0.0257K and 0.1471K

Table 3
for PTB7-Th:PPDI-HD2-T system, PTB7-Th:PPDI-HD-OHD-T system,
Photovoltaic properties for devices based on PTB7-Th:PPDI-HD2-T, PTB7-Th:
PTB7-Th:PPDI-OHD2-T system, respectively. Obviously, along with
PPDI-HD-OHD-T and PTB7-Th:PPDI-OHD2-T.
incorporated alkyloxy side chains into the polymer backbone, the
Acceptors VOC (V) JSC (mA FF (%) PCEb μe (cm2 gradually increased χ values implied the little by little deteriorated
cm− 2)a (%) V− 1 − 1
s )
miscibility, which tallied with improved molecular planarity and
PPDI-HD2-T 0.75 ± 6.04 ± 0.20 39.21 ± 1.78 ± 8.32 × enhanced molecular interaction and also agreed with the later coarse
0.01 (5.95) 0.54 0.12 10− 6
surface morphology [67,68].
PPDI-HD- 0.63 ± 7.06 ± 0.22 46.56 ± 2.08 ± 2.25 ×
OHD-T 0.01 (6.98) 0.65 0.22 10− 5
PPDI-OHD2- 0.65 ± 4.89 ± 0.16 39.20 ± 1.24 ± 7.22 × 3. Conclusion
T 0.01 (4.80) 0.48 0.16 10− 6
a
Integrated current density obtained from EQE curve. In short, three D-A type PDI-based polymeric acceptors, namely,
b
Average values were obtained from 5 independent devices. PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T, utilizing different
flexible side chains (2-hexyldecyl and 2-hexyldecyloxy) modified PDI
for the increased FF from 39.20% to 46.64% and thus improved PCE. unit as acceptor units and thiophene as donor moieties, were synthesized
to study the influence on the absorption, energy level, aggregation in
solution and film state, molecular configuration, ESP, photovoltaic
2.7. Morphological and miscible properties performance and morphology. Influenced by the N–O σ-inductive effect,
as the number of alkyloxy side chain attached into imide N position of
To further gain insight into the influence of flexible side chains of PDI increased, first red-shifted then blue-shifted the maximum absorp­
these PDI-based polymer acceptors on the morphology, the tapping tion peak, first increased then reduced optical bandgap, both gradually
mode atomic force microscope (AFM) was chosen to characterize the down-shifted EHOMO and ELUMO, planarized molecular configuration and
investigated surface topography [78,79]. As exhibited in Fig. 7, values of enhanced aggregation both in solution and film states, and improved
root mean square (RMS) roughness on PTB7-Th:PPDI-HD2-T-, PTB7-Th: photo-stability were found. Interestingly, PPDI-HD-OHD-T bearing
PPDI-HD-OHD-T- and PTB7-Th:PPDI-OHD2-T-based blend films were OHD and HD side chains showed the more complementary absorption
separately observed to be 1.09, 1.12, and 1.24 nm. The gradually with PTB7-Th, enhanced electron mobility and advantaged morphology.
enhanced surface roughness agreed with the gradually planarized mo­ Accordingly, the increased JSC, FF and boosted PCE of 2.08% regardless
lecular configuration and increased molecular aggregation, which was of the decreased VOC in PPDI-HD-OHD-T-based device were obtained,
verified by the later decreased miscibility when alkyloxy side chains which outperformed those in PPDI-HD2-T and PPDI-HD-OHD-based
were bonded into the PDI ring. The middle surface roughness and devices. These experimental results suggested that skillfully tuning the
nano-scaled phase separation in PTB7-Th:PPDI-HD-OHD-T-based de­ side-chain attached into the imide N position of PDI-based polymer
vice could in part account for the enhanced FF and thus improved PCE acceptors can effectively affect the electron distribution, molecular
after incorporating one 2-hexyldecyloxy side chain into imide N position configuration, aggregation and charge mobility, leading to a boosted
of PDI subunit. photovoltaic property in All-PSCs.
To further comprehend the inherent mechanism of the different
flexible side chains affecting the morphology, the contact angle (CA) 4. Experimental section
was applied to ascertain the miscibility and interaction between donor
PTB7-Th and acceptors PPDI-HD2-T, PPDI-HD-OHD-T and PPDI- 4.1. Materials
OHD2-T. The surface CAs of water and ethylene glycol (EG) on the
above-mentioned pure films were measured in Fig. 8, and the related CA All chemicals were obtained from commercial business and directly
data were summarized in Table S6. It was exhibited that the surface applied without further treatment. 1,7-Dibromo-3,4,9,10-perylenetetra­
tension values of pure PPDI-HD2-T, PPDI-HD-OHD-T, PPDI-OHD2-T, carboxylic dianhydride (PTCDABr2) was obtained from Shanghai DiBo
and PTB7-Th films were 31.47, 28.56, 34.67 and 30.30 mN m− 1, Biotechnology Co., Ltd. Donor PTB7-Th (Mn = 17.6 kDa, polydisperse
respectively. Obviously, PPDI-HD-OHD-T-based film bearing different index = 1.70) was obtained from Solarmer Materials Inc. and interlayer
side chains exhibited smaller surface tensions than those of symmetric material PDINO was acquired from Derthon Optoelectronic Materials
PPDI-HD2-T- and PPDI-OHD2-T-based films. Based on the Flory- Science Technology Co. LTD. 2-Hexdecylamine (NH2-HD) [67] and 2,
Huggins theory, surface energy parameter χ D− A was estimated by the 5-bis(trimethyltin)thiophene (TSn) [73] were synthesized in light of
formula: χ = K(γ 0.5 0.5 2
D ‒γ A ) , to quantitatively analyze the miscibility be­ the previous methods.
tween donor and acceptor [80]. Where K is a positive constant, γ D and γ A
are the surface tension of the polymer donor PTB7-Th and polymeric

8
J. Tong et al. Dyes and Pigments 214 (2023) 111236

Fig. 7. AFM height images, phase diagram, and 3D diagram for polymeric acceptors PPDI-HD2-T (a, d and g), PPDI-HD-OHD-T (b, e and h) and PPDI-OHD2-T (c, f
and i).

Fig. 8. Contact angles of polymeric acceptors PPDI-HD2-T, PPDI-HD-OHD-T and PPDI-OHD2-T and donor PTB7-Th.

4.2. Synthesis of comonomers
4.2.1. Synthesis of N-(2-hexyldecyloxy)phthalimide (PI-OHD) [65]
To a solution of N-hydroxyphthalimide (16.64 g, 102 mmol) 100 mL
DMF, 1-bromo-2-hexyldecane (31.2 g, 102 mmol) and Et3N (62.00 g,
613 mmol, 6.0 eq) were slowly added in turn, and the solution altered
from yellow to brown-red. The resulting reacting solution kept stirring
at ambient temperature until the N-hydroxyphthalimide disappeared.
After removing the solvent DMF, the residue was extracted by CH2Cl2
and then washed by water, respectively. Purifying the crude product
using chromatography (petroleum ether (PE) and CH2Cl2 (DCM) with
the volume ratio of 2:1 as eluent) obtained 14.00 g PI-OHD as colourless
oil (Yield, 35%). 1H NMR (500 MHz, CDCl3), δ 7.83‒7.82 (dd, J = 5.5,
3.0 Hz, 2H), 7.75‒7.73 (dd, J = 5.5, 3.0 Hz, 2H), 4.09 (d, J = 6.0 Hz,
2H), 1.81 (br, 1H), 1.53‒1.48 (m, 2H), 1.42‒1.20 (s, 22H), 0.90‒0.86
(m, 6H). Elemental Anal. Calcd for C24H37NO3: C, 74.38%; H, 9.62%; N,
3.61%. Found, C, 74.27%; H, 9.57%; N, 3.72%.
4.2.2. Synthesis of 2-hexyldecyloxyamine (NH2-OHD) [66]
Under Ar, into a solution of PI-OHD (14.00 g, 36 mmol) in 250 mL

9
J. Tong et al.
three-neck flask, 100 mL ethanol was added. Hydrazine hydrate
(N2H4⋅H2O, 2.50 g) was slowly added through the syringe. The resulting
reaction solution was heated and kept refluxing. After the yellow clear
solution muddied and a large of white precipitation formed, another 50
mL ethanol was added again. After disappearance of PI-OHD, the
reacting solution was quenched with H2O. Removing the solvent under
reduced pressure, the residual compound was extracted with DCM then
washed with H2O. Purifying the crude product with chromatography
(PE:DCM = 1:1) obtained 9.38 g NH2-OHD as colourless oil (Yield,
96%).1H NMR (500 MHz, CDCl3) δ 5.32 (s, 2H), 3.55 (d, J = 6.0 Hz, 2H),
1.60 (br, 1H), 1.31‒1.20 (m, 24H), 0.88 (t, J = 7.0 Hz, 6H). Elemental
Anal. Calcd for C16H35NO: C, 74.64%; H, 13.70%; N, 5.44%. Found, C,
74.59%; H, 13.55%; N, 5.58%.
4.2.3. Synthesis of N,N′ -bis(2-hexyldecyl)-(1,7&1,6)-dibromo-3,4,9,10-
perylene diimide (PDI-HD2Br2) [26]
PTCDABr2 (2.00 g, 3.6 mmol) was added to the mixed solvent of 50
mL n-BuOH and 50 mL H2O then kept sonicating for ca. 15 min. Then
3.04 g (12.6 mmol, 3.5 eq) of NH2-HD was added and stirred for over­
night at 80 ◦ C under Ar. At the end, 15 mL concentrated HCl was added
to the above reaction solution at room temperature and was stirred
another 0.5 h. The mixture was extracted with DCM and washed with
water, then dried over anhydrous Na2SO4. Purifying the crude product
with column chromatography (PE:DCM = 1:5) yielded 3.12 g PDI-
HD2Br2 as a red solid (Yield, 86%). M.p., 88–90 ◦ C. 1H NMR (500 MHz,
CDCl3) δ 9.47 (d, J = 8.5 Hz, 2H), 8.91 (s, 2H), 8.68 (d, J = 8.5 Hz, 2H),
4.14 (d, J = 7.5 Hz, 4H), 2.00 (br, 2H), 1.41‒1.20 (m, 48H), 0.86‒0.83
(m, 12H). 13C NMR (125 MHz, CDCl3) δ 163.2, 162.7, 138.2, 138.1,
133.1, 132.9, 132.7, 130.0, 129.2, 128.4, 126.9, 123.2, 122.7, 120.8,
44.9, 31.9, 31.9, 29.7, 29.6, 29.3, 26.5, 26.5, 22.7, 14.15. MS (MALDI-
TOF) m/z: Calcd. for C56H72Br2N2O4: 996.384; [M+H]+ found, 997.686.
Elemental Anal. Calcd for C56H72Br2N2O4: C, 67.46%; H, 7.28%; N,
2.81%. Found, C, 67.23%; H, 7.19%; N, 2.98%.
4.2.4. Synthesis of N-(2-hexyldecyl)-(1,7&1,6)-dibromo-3,4,9,10-
perylene tetracarboxylic acid- 3,4-anhydride-9,10-imide (PDI-HDBr2)
Into a 100 mL three-necked flask of PDI-HD2Br2 (2.00 g, 2 mmol),
30 mL tBuOH and 0.64 g (11 mmol, 5.5 eq) of 85% KOH were added, and
the resulting reaction solution was heated to 90 ◦ C for about 1.5 h. Upon
the disappearance of PDI-HD2Br2, the mixture was cooled to room
temperature then quenched with about 5 mL con. HCl, and continued to
stir for about 0.5 h. The product was extracted with DCM, then dried
over Na2SO4. Purifying the crude product with column chromatography
(AcOH:DCM = 1:10) acquired 1.24 g title compound as red solid (Yield,
80%). M.p., 98–102 ◦ C. 1H NMR (500 MHz, CDCl3) δ 9.54 (dd, J = 8.0,
2.5 Hz, 2H), 8.95 (s, 2H), 8.72 (dd, J = 8.0, 1.0 Hz, 2H), 4.14 (d, J = 7.5
Hz, 2H), 2.00 (br, 1H), 1.40‒1.25 (m, 24H), 0.85 (m, 6H). Elemental
Anal. Calcd for C40H39Br2NO5: C, 62.11%; H, 5.08%; N, 1.81%. Found,
C, 62.06%; H, 4.98%; N, 1.94%.
4.2.5. Synthesis of N-(2-hexyldecyl)-N’-(2-hexyldecyloxy)-(1,7&1,6)-
dibromo-3,4,9,10-perylene diimide (PDI-HD-OHDBr2)
Into a 250 mL three-necked flask, PDI-HDBr2 (0.80 g, 1.03 mmol)
was added to the mixed solvent (30 mL nBuOH and 30 mL H2O) then
kept sonicating for about 15 min. Then 0.53 g NH2-OHD (2.06 mmol,
2.0 eq) was added and the reacting mixture heated to 80 ◦ C. The reacting
mixture was extracted with DCM and washed with H2O, then dried over
Na2SO4. Purifying crude product with column chromatography (PE:
DCM = 1:2) yielded 0.67 g PDI-HD-OHDBr2 as red solid (Yield, 65%).
M.p., 117–120 ◦ C. 1H NMR (500 MHz, CDCl3) δ 9.49 (d, J = 8.5 Hz, 2H),
8.94 (s, 2H), 8.72 (d, J = 8.5 Hz, 2H), 4.16 (d, J = 5.5 Hz, 4H), 1.92 (br,
2H), 1.62‒1.58 (m, 4H), 1.50‒1.25 (m, 44H), 0.92‒0.88 (m, 12H). 13C
NMR (125 MHz, CDCl3) δ 159.7, 159.2, 138.1, 133.3, 133.1, 130.3,
129.3, 128.8, 126.2, 123.5, 123.1, 121.0, 80.0, 37.7, 31.9, 31.9, 30.0,
29.7, 29.7, 29.4, 26.8, 26.8, 22.7, 14.2. Elemental Anal. Calcd for
C56H72Br2N2O5: C, 66.40%; H, 7.16%; N, 2.77%. Found, C, 66.28%; H,
10
Dyes and Pigments 214 (2023) 111236
7.08%; N, 2.85%.
4.2.6. Synthesis of N,N′ -bis(2-hexyldecyloxy)-1,7-dibromo-3,4,9,10-
perylene diimide (PDI-OHD2Br2)
In a 250 mL three-necked flask, PTCDABr2 (1.00 g, 1.82 mmol) was
added to the mixted solvent (30 mL nBuOH and 30 mL H2O) then kept
sonicating for about 15 min. Then NH2-OHD (1.64 g, 6.38 mmol, 3.5 eq)
was added then heated to 80 ◦ C. The reacting mixture was extracted
with DCM then washed with H2O, then dried over Na2SO4. Purifying the
crude product with column chromatography (PE:DCM = 2:5) got 1.07 g
PDI-OHD2Br2 as red solid (Yield, 57%). M.p., 135–138 ◦ C. 1H NMR
(500 MHz, CDCl3) δ 9.48 (d, J = 8.5 Hz, 2H), 8.93 (s, 2H), 8.72 (d, J =
8.5 Hz, 2H), 4.16 (d, J = 5.5 Hz, 4H), 1.92 (br, 2H), 1.63‒1.58 (m, 4H),
1.50‒1.25 (m, 44H), 0.90‒0.88 (m, 12H). 13C NMR (125 MHz, CDCl3) δ
159.7, 159.2, 138.1, 133.3, 133.1, 130.3, 129.3, 128.8, 126.2, 123.6,
123.2, 121.0, 80.0, 37.7, 32.0, 31.9, 31.2, 30.1, 29.7, 29.7, 29.4, 26.8,
26.8, 22.7, 14.2. MS (MALDI-TOF) m/z: Calcd. for C56H72Br2N2O6:
1028.374; [M+Na]+ found, 1051.631. Elemental Anal. Calcd for
C56H72Br2N2O6: C, 65.37%; H, 7.05%; N, 2.72%. Found, C, 65.29%; H,
7.01%; N, 2.79%.
4.2.7. Synthesis of poly[(N,N′ -bis(2-hexyldecyl)-3,4,9,10-perylene
diimide-1,7-diyl)-alt- (thiophene-2,5-diyl)] (PPDI-HD2-T)
Purified PDI-HD2Br2 (149.5 mg, 0.15 mmol), TSn (61.3 mg, 0.15
mmol), 6 mL degassed toluene and 0.7 mL DMF were added to a 25 mL
two-neck flask. After bubbling the resulting mixture with Argon for 20
min, 1.5 mg Pd2(dba)3 and 2.5 mg of P(o-tolyl)3 was added. The reacting
mixture was bubbled again and lasted for another 20 min in order to
drive out the residual O2. The reacting solution was heated to 110 ◦ C
under Ar and lasted for 48 h. Finally, the end-capped treatment was
performed with 2-tributyltinthiohene and 2-bromothiophene. The
reacting solution was poured into 300 mL MeOH and the polymeric
acceptor was collected by filtration. Purifying the crude product with
Soxhlet extraction utilizing MeOH, hexane, and toluene as extractants
and condensing the toluene fraction into about 6 mL then precipitating
into 300 mL MeOH obtained 105.2 mg black solid as title polymer (Y =
76%). 1H NMR (500 MHz, CDCl3) δ 8.71 (br, hydrogen of PDI ring), 8.53
(br, hydrogen of PDI ring), 8.41 (br, hydrogen of PDI ring), 7.41 (br,
hydrogen of thiophene), 7.18 (br, hydrogen of thiophene), 4.12 (m,
N–CH2), 1.98 (br, >CH‒), 1.50‒1.25 (m, –CH2‒), 0.90‒0.78 (m, CH3).
Mn = 15.7 kDa, Mw = 29.0 kDa, polydisperse index = 1.85.
4.2.8. Synthesis of poly[(N-(2-hexyldecyl)-N’-(2-hexyldecyloxy)-
3,4,9,10-perylene diimide-(1,7&1,6)-diyl)-alt-(thiophene-2,5-diyl)]
(PPDI-HD-OHD-T)
Synthetic procedure of PPDI-HD-OHD-T was similar with that of
PPDI-HD2-T and obtained 76.5 mg purple-black solid (Y = 74%). 1H
NMR (500 MHz, CDCl3) δ 8.79 (br, hydrogen of PDI ring), 8.42 (br,
hydrogen of PDI ring), 7.47 (br, hydrogen of thiophene), 7.02 (br,
hydrogen of thiophene), 4.15 (br, N–CH2 and N–O–CH2), 1.88 (br,
>CH‒), 1.60‒1.25 (m, –CH2‒), 0.88‒0.84 (m, CH3). Mn = 13.8 kDa,
Mw = 27.3 kDa, polydisperse index = 1.98.
4.2.9. Synthesis of poly[(N,N′ -bis(2-hexyldecyloxy)-3,4,9,10-perylene
diimide-(1,7&1,6)- diyl)-alt-(thiophene-2,5-diyl)] (PPDI-OHD2-T)
Synthetic procedure of PPDI-OHD2-T was similar with that of PPDI-
HD2-T and obtained 101 mg black solid (Y = 71%). 1H NMR (500 MHz,
CDCl3) δ 8.72 (br, hydrogen of PDI ring), 8.41 (br, hydrogen of PDI ring),
7.43 (br, hydrogen of thiophene), 7.05 (br, hydrogen of thiophene), 4.15
(m, N–O–CH2), 1.91 (br, >CH‒), 1.60‒1.25 (m, –CH2‒), 0.90‒0.83 (m,
CH3). Mn = 14.3 kDa, Mw = 14.3 kDa, polydisperse index = 2.04.
CRediT authorship contribution statement
Junfeng Tong: Conceptualization, Investigation, Writing – original
draft. Zheyu Li: Writing , Investigation. Yubo Huang: Investigation.
J. Tong et al.
Yan Wang: Investigation. Lichun Zhang: Investigation. Lili An:
Investigation. Pengzhi Guo: Validation. Chunyan Yang: Supervision.
Jianfeng Li: Supervision. Yangjun Xia: Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgements
The work was financially supported by National Natural Science
Foundation of China (62064006, 52262026, 62164007 and 61964010),
the Natural Science Foundation of Gansu Province (20JR5RA403), In­
dustrial support plan project of colleges and universities in Gansu
Province (No: 2020C-07 and 2021CYZC-19).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.dyepig.2023.111236.
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