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\begin{document}

\title{The Combination of S[?]N and S[?]Cl Noncovalently Conformational Locks for
Constructing High-Planarity and Low-Cost Non-fused-Ring Electron
Acceptors}



\author[1]{Ziyang Han}%
\author[1]{Congqi Li}%
\author[1]{Xiaobin Gu}%
\author[1]{Xiao Han}%
\author[1]{Sixuan Wang}%
\author[1]{Yanan Wei}%
\author[1]{Jinhua Gao}%
\author[2]{Zhixiang Wei}%
\author[1]{Yunhao Cai}%
\author[1]{Xin Zhang}%
\author[1]{Hui Huang}%
\affil[1]{University of the Chinese Academy of Sciences}%
\affil[2]{National Center for Nanoscience and Technology}%


\vspace{-1em}



  
  \date{May 22, 2024}


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\selectlanguage{english}
\begin{abstract}
By employing thiazole and 4-chlorothiazole as the A' units, two
A-D-A'-D-A type nonfused-ring electron acceptors (NFREAs) \textbf{Tz-H}
and \textbf{Tz-Cl} were designed and synthesized. Replacing thiazole in
\textbf{Tz-H} with 4-chlorothiazole can not only remarkably shorten the
synthetic route through C-H direct arylation but also enhance molecular
planarity with the simultaneous incorporation of S\selectlanguage{ngerman}···N and S···Cl
non-covalently conformational locks (NoCLs). The photovoltaic devices
based on PM6:\textbf{Tz-Cl} exhibited a power conversion efficiency as
high as 11.10\%, much higher than that of PM6:\textbf{Tz-H} (6.41\%),
mainly due to more efficient exciton dissociation, better and more
balanced carrier mobility, less charge recombination, and more favorable
morphology. These findings demonstrate the great potential of NoCLs in
achieving low-cost and high-performance NFREAs.%
\end{abstract}\selectlanguage{ngerman}%



\sloppy


\textbf{Cite this paper:}\emph{Chin. J. Chem.} \textbf{2022} , \emph{40}
, XXX---XXX. \textbf{DOI: 10.1002/cjoc.202200XXX}

The Combination of S[?]N and S[?]Cl Noncovalently Conformational Locks for
Constructing High-Planarity and Low-Cost Nonfused-Ring Electron
Acceptors\textsuperscript{+}

Ziyang Han,\emph{\textsuperscript{a}} Congqi
Li,\emph{\textsuperscript{a}}Xiaobin Gu,\emph{\textsuperscript{a}} Xiao
Han,\emph{\textsuperscript{a}} Sixuan
Wang,\emph{\textsuperscript{a}}Yanan Wei,\emph{\textsuperscript{a}}
Jinhua Gao,\emph{\textsuperscript{a}} Zhixiang
Wei,\emph{\textsuperscript{b}}Yunhao Cai,\emph{\textsuperscript{a}} Xin
Zhang*\textsuperscript{,\emph{a}} and Hui
Huang*\textsuperscript{,\emph{a}}

\textsuperscript{a} College of Materials Science and Opto-Electronic
Technology \& Center of Materials Science and Optoelectronics
Engineering \& CAS Center for Excellence in Topological Quantum
Computation \& CAS Key Laboratory of Vacuum Physics, University of
Chinese Academy of Sciences, Beijing 100049, China\textsuperscript{b}
Center for Excellence in Nanoscience (CAS) \& Key Laboratory of
Nanosystem and Hierarchical Fabrication (CAS), National Center for
Nanoscience and Technology, Beijing 100190, China\selectlanguage{english}
\begin{longtable}[]{@{}l@{}}
\toprule
\textbf{Comprehensive Summary}\tabularnewline
\midrule
\endhead
By employing thiazole and 4-chlorothiazole as the A' units, two
A-D-A'-D-A type nonfused-ring electron acceptors (NFREAs) \textbf{Tz-H}
and \textbf{Tz-Cl} were designed and synthesized. Replacing thiazole in
\textbf{Tz-H} with 4-chlorothiazole can not only remarkably shorten the
synthetic route through C-H direct arylation but also enhance molecular
planarity with the simultaneous incorporation of S\selectlanguage{ngerman}···N and S···Cl
noncovalently conformational locks (NoCLs). The photovoltaic devices
based on PM6:\textbf{Tz-Cl} exhibited a power conversion efficiency as
high as 11.10\%, much higher than that of PM6:\textbf{Tz-H} (6.41\%),
mainly due to more efficient exciton dissociation, better and more
balanced carrier mobility, less charge recombination, and more favorable
morphology. These findings demonstrate the great potential of NoCLs in
achieving low-cost and high-performance NFREAs.\tabularnewline
\bottomrule
\end{longtable}\selectlanguage{ngerman}\selectlanguage{english}
\begin{longtable}[]{@{}l@{}}
\toprule
\textbf{Keywords}\tabularnewline
\midrule
\endhead
Organic solar cells \textbar{} Nonfused-ring electron acceptors
\textbar{} Noncovalently conformational locks \textbar{} High-planarity
and low-cost acceptors \textbar{} 4-Chlorothiazole\tabularnewline
\bottomrule
\end{longtable}

\section*{}

{\label{section}}

Background and Originality Content

In recent years, the development of organic solar cells (OSCs) has
largely benefited from the revolution of non-fullerene acceptors,
especially fused-ring electron acceptors (FREAs) with the
acceptor-donor-acceptor (A-D-A) architecture, which were pioneered by
Zhan et al. in 2015.\textsuperscript{{[}1-3{]}} Later in early 2019, Zou
et al. reported a new generation of A-DA'D-A structured FREAs
(represented by Y6), containing electron-deficient units in the
fused-ring cores.\textsuperscript{{[}4, 5{]}} Due to the unique
structural feature, FREAs possess superior absorption property and tight
intermolecular \selectlanguage{greek}π--π \selectlanguage{english}stacking in common.\textsuperscript{{[}6{]}} With
the continuous efforts on molecular tailoring and device engineering,
the power conversion efficiencies (PCEs) of the state-of-the-art single
junction OSCs have exceeded 19\%.\textsuperscript{{[}7-14{]}} However,
due to the remarkable structural feature of highly fused conjugated
backbones, FREAs generally require complicated synthetic approaches and
suffer from low yields and high product costs, which may severely hinder
their large-scale applications.

To address the disadvantage of FREAs, an alternative strategy for
low-cost electron acceptors was proposed, namely nonfused-ring electron
acceptors (NFREAs).\textsuperscript{{[}15{]}} In general, this novel
type of acceptors shares an unfused central core (a simply fused or even
completely unfused \selectlanguage{greek}π-\selectlanguage{english}conjugated core), thus making the synthesis route
more concise.\textsuperscript{{[}16-21{]}} More importantly, the
noncovalently conformational locks (NoCLs) strategy is generally
introduced in the molecular design of NFREAs, which can effectively
restrict the rotation of single bonds and reduce conformational isomers
raised from the unfused-ring cores, thus improving the molecular
planarity and rigidity.\textsuperscript{{[}22-26{]}} Therefore, NFREAs
possess a simple-structured yet co-planar conjugated backbone, opening
the opportunity for constructing cost-effective acceptor
materials.\textsuperscript{{[}27-29{]}} Regarded as tailoring from
A-DA'D-A type FREAs, A-D-A'-D-A structured NFREAs have received much
attention recently. Due to the key role of the A' unit in regulating
light-harvest ability, energy levels, intramolecular conformation, and
intermolecular packing behaviors, a lot of work has been devoted to the
selection of A' units, including benzo{[}\emph{c}
{]}{[}1,2,5{]}thiadiazole,\textsuperscript{{[}30, 31{]}}2\emph{H}
-benzo{[}\emph{d} {]}{[}1,2,3{]}triazole,\textsuperscript{{[}32, 33{]}}
thieno{[}3,4-\emph{c} {]}pyrrole-4,6-dione,\textsuperscript{{[}34,
35{]}} and benzo-{[}1,2-\emph{c} :4,5-\emph{c'}
{]}dithiophene-4,8-dione.\textsuperscript{{[}36, 37{]}} However, it is
still challenging to rationally choose an electron-withdrawing motif as
the A' unit.

Thiazole is a widely-used electron-deficient heteroaromatic ring due to
its electron-withdrawing nitrogen of imine
(C=N),\textsuperscript{{[}38{]}} which has been employed in constructing
organic semiconductors for optoelectronics, such as
OSCs,\textsuperscript{{[}39{]}} organic field-effect transistors
(OFETs),\textsuperscript{{[}40{]}} and organic light-emitting diodes
(OLEDs).\textsuperscript{{[}41{]}} Compared with thiazole,
4-chlorothiazole should be a more electron-deficient unit, which is
expected to build organic conjugated molecules with deep-lying highest
occupied molecular orbital (HOMO) energy levels. Particularly, the N and
Cl atoms in 4-chlorothiazole may be able to form S\selectlanguage{ngerman}···N and S···Cl NoCLs
with neighboring thiophene units to enhance the molecular planarity.
Therefore, 4-chlorothiazole is an excellent candidate as the A\selectlanguage{english}' unit to
construct high-planarity and low-cost NFREAs.

Herein, thiazole and 4-chlorothiazole were utilized as the A\selectlanguage{english}' units to
construct two A-D-A\selectlanguage{english}'-D-A type NFREAs, namely \textbf{Tz-H} and
\textbf{Tz-Cl} , respectively (Figure 1a). Compared with \textbf{Tz-H} ,
\textbf{Tz-Cl}possessed a facile and concise synthesis, due to the
unexpectedly C-H direct arylation of 2,5-dibromo-4-chlorothiazole. Both
density function theory (DFT) calculations and single-crystal X-ray
diffraction (SC-XRD) data revealed that the simultaneous incorporation
of S***N and S***Cl NoCLs can provide a more planar conjugated
backbones, and thus a more compact and ordered packing than the sole
introduction of S***N NoCLs. When blending with the polymer donor PM6,
the \textbf{Tz-Cl} -based blend film afforded higher exciton
dissociation efficiency, more balanced charge mobility, lower
recombination loss, shorter charge extraction time, and more favorable
morphology. Therefore, a PCE of 11.10\% was achieved for \textbf{Tz-Cl}
-based devices, much higher than that of the\textbf{Tz-H} counterpart
(6.41\%). This work demonstrated the potential of NoCLs to construct
low-cost NFREAs.

Results and Discussion

Synthesis and characterization

The synthesis routes of the two NFREAs were shown in Scheme S1, and the
detailed synthesis
procedures,\textsuperscript{1}H-/\textsuperscript{13}C-NMR spectrometry,
and mass spectrometry were given in Supporting Information. Initially,
we tried to obtain the dialdehyde intermediate \textbf{4} from
2,5-dibromothiazole (\textbf{1} ) and compound \textbf{6} by
Pd(0)-catalyzed C-H activation, but failed. Thus, we utilized
compound\textbf{1} with 2 equivalents of mono-organotin compound
(\textbf{2} ) to afford a nonfused-type conjugated core (\textbf{3} ),
followed by the Vilsmeier-Haack reaction to convert dialdehyde
intermediate \textbf{4} . Different from the chloro-free thiazole
derivation, 2,5-dibromo-4-chlorothiazole (\textbf{5} ) can unexpectedly
undergo a two-fold C-H activation with compound\textbf{6} to directly
afford dialdehyde intermediate \textbf{7} . Finally, \textbf{Tz-H} and
\textbf{Tz-Cl} was obtained through Knoevenagel condensation between the
dialdehyde intermediate (\textbf{4}or \textbf{7} ) and
2-(5,6-dichloro-3-oxo-2,3-dihydro-1\emph{H}
-inden-1-ylidene)malononitrile (IC-2Cl). Obviously, the synthetic route
for \textbf{Tz-Cl} is more concise, which may be beneficial to reducing
the production cost. Both\textbf{Tz-H} and \textbf{Tz-Cl} showed good
solubility in common organic solvents, such as chloroform, tetrahedron,
and chlorobenzene.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image3/image3}

\end{center}
\end{figure}

\par\null

\textbf{Figure 1} (a) Chemical structures and (b) optimized geometries
(top: top view; bottom: side view) of the two NFREAs. (c) Single crystal
structures of the two model compounds TzDT-Br and TzClDT-Br. (d) GIWAXS
patterns of neat \textbf{Tz-H} and \textbf{Tz-Cl} films and (e) the
corresponding scattering profiles in the out-of-plane (solid line) and
in-plane (dashed line) directions.

The optimized molecular geometries of \textbf{Tz-H} and
\textbf{Tz-Cl}with simplified side-chains were investigated with DFT
calculations at the B3LYP/6-31G(d,p) level. As shown in Figure 1b, both
\textbf{Tz-H}and \textbf{Tz-Cl} possessed near-coplanar \selectlanguage{greek}π-\selectlanguage{english}conjugated
backbones with small dihedral angles (\selectlanguage{greek}\emph{θ} \selectlanguage{english}\textsubscript{1}
and\selectlanguage{greek}\emph{θ} \selectlanguage{english}\textsubscript{2}). Especially, \textbf{Tz-Cl} exhibited
both\selectlanguage{greek}\emph{θ} \selectlanguage{english}\textsubscript{1} and \selectlanguage{greek}\emph{θ} \selectlanguage{english}\textsubscript{2} of near
0\selectlanguage{ngerman}°, which is favorable for the intermolecular \selectlanguage{greek}π--π \selectlanguage{english}stacking and charge
transport. The intramolecular distance between the sulfur and nitrogen
atoms (\emph{d} \selectlanguage{ngerman}\textsubscript{intra, S···N}) were calculated to be
\textasciitilde{}3.04 and \textasciitilde{}3.05 Å for \textbf{Tz-H}
and\textbf{Tz-Cl} , respectively, and the intramolecular distance
between the sulfur and chlorine atoms (\emph{d} \textsubscript{intra,
S···Cl}) was calculated to be \textasciitilde{}3.21 Å for \textbf{Tz-Cl}
, much shorter than the sum of the van der Waals radius (\emph{r}
\textsubscript{w, S···N} = 3.35 Å and \emph{r} \textsubscript{w, S···Cl}
= 3.65 Å), indicating the existence of S···N and S···Cl NoCLs. Thus,
\textbf{Tz-Cl} possessed a more planar conformation mainly due to the
incorporation of multiple NoCLs.

To gain more structural information on the thiazole- and
4-chlorothiazole-based NFREAs, the single crystals of two model
compounds TzDT-Br and TzClDT-Br were grown by solvent vapor diffusion
using chloroform/methanol (Table S1). As shown in Figure 1c, the single
crystal structure of TzClDT-Br shared a more co-planar conformation with
dihedral angles \selectlanguage{greek}\emph{θ} \selectlanguage{english}\textsubscript{1} of 1.8\selectlanguage{ngerman}° and\selectlanguage{greek}\emph{θ}
\selectlanguage{english}\textsubscript{2} of 3.8\selectlanguage{ngerman}°, much smaller than those of 2.1° and 5.5° in
TzDT-Br. In addition, the short \emph{d} \textsubscript{intra, S···N}
and \emph{d} \textsubscript{intra, S···Cl} again indicated that the
planar conformations could be enforced by S···N and S···Cl NoCLs. Such a
planar conjugated backbone of TzClDT-Br is expected to favor the
stacking of \textbf{Tz-Cl} .

\textbf{Table 1} Basic properties of \textbf{Tz-H} and \textbf{Tz-Cl}\selectlanguage{english}
\begin{longtable}[]{@{}lllll@{}}
\toprule
\begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
NFREAs\strut
\end{minipage} & \begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
\selectlanguage{greek}\emph{λ}\selectlanguage{english}\textsubscript{abs.max}\textsuperscript{sol.} {[}nm{]}\strut
\end{minipage} & \begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
\selectlanguage{greek}\emph{λ}\selectlanguage{english}\textsubscript{abs.max}\textsuperscript{film} {[}nm{]}\strut
\end{minipage} & \begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
\emph{E}\textsubscript{g}\textsuperscript{opt} {[}eV{]}\strut
\end{minipage} & \begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
\emph{E}\textsubscript{HOMO}/\emph{E}\textsubscript{LUMO} {[}eV{]}\strut
\end{minipage}\tabularnewline
\midrule
\endhead
\begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
\textbf{Tz-H}\strut
\end{minipage} & \begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
717\strut
\end{minipage} & \begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
711, 780\strut
\end{minipage} & \begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
1.41\strut
\end{minipage} & \begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
-5.61/-3.94\strut
\end{minipage}\tabularnewline
\begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
\textbf{Tz-Cl}\strut
\end{minipage} & \begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
718\strut
\end{minipage} & \begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
700, 768\strut
\end{minipage} & \begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
1.43\strut
\end{minipage} & \begin{minipage}[t]{0.17\columnwidth}\raggedright\strut
-5.65/-3.97\strut
\end{minipage}\tabularnewline
\bottomrule
\end{longtable}

The packing behavior in the neat films were investigated by
two-dimensional grazing incidence wide-angle X-ray scattering
(2D-GIWAXS). As shown in Figures 1c and 1d, the neat film
of\textbf{Tz-H} exhibited a bi-modal packing as supported by the (010)
\selectlanguage{greek}π--π \selectlanguage{english}stacking peaks (\emph{d} \textsubscript{010} = 3.61 \selectlanguage{ngerman}Å) along both
the out-of-plane (OOP) and the in-plane (IP) directions. In contrast, a
dominant (010) \selectlanguage{greek}π--π \selectlanguage{english}stacking peak in the OOP direction (\emph{q}
\textsubscript{z} = 1.75 \selectlanguage{ngerman}Å\selectlanguage{english}\textsuperscript{-1},\emph{d}
\textsubscript{010} = 3.58 A) was observed in the \textbf{Tz-Cl}thin
film, indicating a predominantly face-on orientation. Besides, the
crystal coherence lengths (CCLs) for (010) diffraction peaks along the
OOP direction were 1.65 and 1.82 nm for \textbf{Tz-H} and\textbf{Tz-Cl}
, respectively, as determined by the Scherrer equation. The reduced \selectlanguage{greek}π--π
\selectlanguage{english}stacking distance and enhanced CCLs in the neat film of\textbf{Tz-Cl}
indicated a more compact and ordered packing, which may be attributed to
the improved backbone coplanarity by the simultaneous incorporation of
S\selectlanguage{ngerman}···N and S···Cl NoCLs.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image4/image4}

\end{center}
\end{figure}

\textbf{Figure 2} Normalized dilute solution (a) and thin film (b)
optical absorption spectra of \textbf{Tz-H} and \textbf{Tz-Cl} .

The UV-vis absorption spectra of the two NFREAs in dilute chloroform
solution and thin film were shown in Figures 2a and 2b, and the
corresponding optical parameters were summarized in Table 1. Due to
their similar chemical structures, both \textbf{Tz-H} and
\textbf{Tz-Cl}exhibited almost identical solution absorption spectra
with the maximum peaks located at 717 and 718 nm, respectively. In solid
state,\textbf{Tz-H} and \textbf{Tz-Cl} possessed a strong absorption in
the region of 600-850 nm, showing a red-shift of \textasciitilde{} 50 nm
relative to that in solution state (724 nm). Specially in the
S\textsubscript{0}-S\textsubscript{1} band, the absorption intensity of
0--0 vibronic transition was relatively lower than that of 0--1
transition, indicating the formation of H-aggregates in the two NFREA
films.\textsuperscript{{[}42{]}} The optical bandgaps of
\textbf{Tz-H}and \textbf{Tz-Cl} were 1.41 and 1.43 eV, respectively,
according to the equation: \emph{E}
\textsubscript{g}\textsuperscript{opt} = 1240/\selectlanguage{greek}\emph{λ}
\selectlanguage{english}\textsubscript{onset}. According to the cyclic voltammetry (CV)
measurements, the HOMO and the lowest unoccupied molecular orbital
(LUMO) energy levels of \textbf{Tz-H} and \textbf{Tz-Cl}were estimated
to be -5.62/-3.94 and -5.65/-3.97 eV, respectively (Figure S1 and Table
1). Compared with \textbf{Tz-H} ,\textbf{Tz-Cl} possessed slightly
lower-lying HOMO/LUMO energy levels, which should be attributed to the
introduction of electron-withdrawing chlorine atom.

Photovoltaic properties

To investigate the photovoltaic performance of the two NFREAs, OSC
devices with an conventional device structure of ITO/PEDOT:PSS/active
layer/PDIN/Ag based on PM6:\textbf{Tz-H} and PM6:\textbf{Tz-Cl} blends
were fabricated. The detailed optimization process of \textbf{Tz-H} -
and\textbf{Tz-Cl} -based photovoltaic devices was shown in Tables S2 and
S3, including the weight ratio of donor and acceptor as well as the
content of additive. The optimized device based on PM6:\textbf{Tz-H}
showed an inferior PCE of 6.41\%, with an open-circuit voltage (\emph{V}
\textsubscript{oc}) of 0.838 V, a short-circuit current density
(\emph{J} \textsubscript{sc}) of 15.74 mA cm\textsuperscript{-2}, and a
fill factor (FF) of 48.57\% (Figure 3a and Table 2). Impressively,
\textbf{Tz-Cl} -based device exhibited a much higher PCE of 11.10\%,
with simultaneously improved\emph{V} \textsubscript{oc} (0.841 V),
\emph{J} \textsubscript{sc} (20.71 mA cm\textsuperscript{-2}), and FF
(63.72\%). To further confirm the accuracy of the \emph{J}
\textsubscript{sc} values, the external quantum efficiency (EQE) spectra
of the devices were shown in Figure 3b. The integrated \emph{J}
\textsubscript{sc} values obtained from the EQE responses were 15.61 and
20.27 mA cm\textsuperscript{-2} for\textbf{Tz-H} - and \textbf{Tz-Cl}
-based devices, respectively, which were well consistent with the
\emph{J} -\emph{V} measurements.

\textbf{Table 2} Photovoltaic parameters of OSCs based on PM6:NFREAs
under AM1.5G illumination, 100 mW cm\textsuperscript{-2}.\selectlanguage{english}
\begin{longtable}[]{@{}lllll@{}}
\toprule
\begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
Active layers\strut
\end{minipage} & \begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
\emph{V}\textsubscript{oc}\emph{\textsuperscript{a}} {[}V{]}\strut
\end{minipage} & \begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
\emph{J}\textsubscript{sc} {[}mA cm\textsuperscript{-2}{]}\strut
\end{minipage} & \begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
FF {[}\%{]}\strut
\end{minipage} & \begin{minipage}[b]{0.19\columnwidth}\raggedright\strut
PCE {[}\%{]}\strut
\end{minipage}\tabularnewline
\midrule
\endhead
\begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
PM6:\textbf{Tz-H}\strut
\end{minipage} & \begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
0.838 (0.840\selectlanguage{ngerman}±0.001)\strut
\end{minipage} & \begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
15.74 (15.79\selectlanguage{ngerman}±0.29)\strut
\end{minipage} & \begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
48.57 (46.80\selectlanguage{ngerman}±1.23)\strut
\end{minipage} & \begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
6.41 (6.20\selectlanguage{ngerman}±0.11)\strut
\end{minipage}\tabularnewline
\begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
PM6:\textbf{Tz-Cl}\strut
\end{minipage} & \begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
0.841 (0.840\selectlanguage{ngerman}±0.001)\strut
\end{minipage} & \begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
20.71 (20.73\selectlanguage{ngerman}±0.44)\strut
\end{minipage} & \begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
63.72 (62.66\selectlanguage{ngerman}±1.23)\strut
\end{minipage} & \begin{minipage}[t]{0.19\columnwidth}\raggedright\strut
11.10 (10.91\selectlanguage{ngerman}±0.12)\strut
\end{minipage}\tabularnewline
\bottomrule
\end{longtable}\selectlanguage{ngerman}

\emph{\textsuperscript{a}} The average values shown in parentheses were
obtained from 15 devices.

To further understand the changes in above-mentioned photovoltaic
properties, charge dynamics were systematically investigated. The
photocurrent density (\emph{J} \textsubscript{ph}) versus effective
voltage (\emph{V} \textsubscript{eff}) curves were firstly measured to
explore the charge generation and extraction mechanism.
Generally,\emph{J} \textsubscript{ph} is defined as \emph{J}
\textsubscript{L} \selectlanguage{english}-\emph{J} \textsubscript{D}, where \emph{J}
\textsubscript{L} and\emph{J} \textsubscript{D} are the photocurrent
densities under illumination and in the dark conditions,
respectively.\emph{V} \textsubscript{eff} can be defined as\emph{V}
\textsubscript{eff} = \emph{V} \textsubscript{0} \selectlanguage{english}-\emph{V}
\textsubscript{bias}, where \emph{V} \textsubscript{0} is the voltage at
which \emph{J} \textsubscript{ph} = 0 and\emph{V} \textsubscript{bias}
is the applied voltage.\textsuperscript{{[}43{]}} Thus, the exciton
dissociation probability can be calculated as the ratio of\emph{J}
\textsubscript{ph}/\emph{J} \textsubscript{sat}, where\emph{J}
\textsubscript{sat} is the saturation photocurrent density. As shown in
Figure 3c, the \emph{P} \textsubscript{diss} values of\textbf{Tz-H} -
and \textbf{Tz-Cl} -based devices were calculated to be 91.7\% and
96.1\%, respectively. The results demonstrated that the\textbf{Tz-Cl}
-based device exhibited a higher exciton dissociation efficiency, which
was well consistent with the higher\emph{J} \textsubscript{sc} value of
20.71 mA cm\selectlanguage{english}\textsuperscript{-2}.

To investigate the charge transport properties in the active layers,
hole and electron mobilities were measured by the space charge limited
current (SCLC) method. As shown in Figure S2, the hole (\selectlanguage{greek}\emph{μ}
\selectlanguage{english}\textsubscript{h}) and electron (\selectlanguage{greek}\emph{μ} \selectlanguage{english}\textsubscript{e}) mobilities
of \textbf{Tz-H} -based blend film were estimated to be 2.35 \selectlanguage{ngerman}×
10\selectlanguage{english}\textsuperscript{-5} and 4.06 x
10\textsuperscript{-5}cm\textsuperscript{2} V\selectlanguage{english}\textsuperscript{-1}
s\selectlanguage{english}\textsuperscript{-1} with a\selectlanguage{greek}\emph{μ} \selectlanguage{english}\textsubscript{h}/\selectlanguage{greek}\emph{μ}
\selectlanguage{english}\textsubscript{e} ratio of 0.58. In contrast, \textbf{Tz-Cl} -based
blend film exhibited not only enhanced (5.54 \selectlanguage{ngerman}× 10\selectlanguage{english}\textsuperscript{-5}
and 5.47 x 10\textsuperscript{-5}cm\textsuperscript{2}
V\selectlanguage{english}\textsuperscript{-1} s\selectlanguage{english}\textsuperscript{-1}) but also balanced (\selectlanguage{greek}\emph{μ}
\selectlanguage{english}\textsubscript{h}/\selectlanguage{greek}\emph{μ} \selectlanguage{english}\textsubscript{e} = 1.01) charge mobilities,
which contributed to the observed higher\emph{J} \textsubscript{sc} and
FF in the PM6:\textbf{Tz-Cl} -based photovoltaic device. In addition,
the charge recombination process was investigated by measuring the light
intensity (\emph{P} \textsubscript{light}) dependent \emph{J}
\textsubscript{sc}. The relationship between \emph{P}
\textsubscript{light} and\emph{J} \textsubscript{sc} follows the formula
of\emph{J} \textsubscript{sc} [?]\emph{P}
\textsubscript{light}\selectlanguage{greek}\emph{\textsuperscript{α}} . \selectlanguage{english}The exponent\selectlanguage{greek}\emph{α}
\selectlanguage{english}value approaches to unit, when free charge carriers are almost swept out
and collected at the electrodes. As shown in Figure 3d, the\selectlanguage{greek}\emph{α}
\selectlanguage{english}value was estimated to be 0.952 for the \textbf{Tz-Cl} -based device
under the short-circuit condition, which is a little higher than that of
PM6:\textbf{Tz-H} (0.927). The higher \selectlanguage{greek}\emph{α} \selectlanguage{english}for the\textbf{Tz-Cl}
-based device indicated its weaker bimolecular recombination that may
contribute to the higher\emph{J} \textsubscript{sc} and FF relative to
the \textbf{Tz-H} -based device.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image5/image5}

\end{center}
\end{figure}

\textbf{Figure 3} (a) \emph{J} -\emph{V} characteristics, (b) EQE
responses, (c) \emph{J} \textsubscript{ph}-\emph{V} \textsubscript{eff},
(d) \emph{J} \textsubscript{sc}-\emph{P} \textsubscript{light}, (e) TPC,
and (f) TPV measurements of the optimized OSCs based on
PM6:\textbf{Tz-H} and PM6:\textbf{Tz-Cl} .

To further understand the charge recombination and extraction processes,
transient photocurrent (TPC) and transient photovoltage (TPV)
measurements were carried out. As presented in Figure 3e, the charge
sweep-out times under the short-circuit condition were roughly estimated
to be 0.97 and 0.84 \selectlanguage{greek}μ\selectlanguage{english}s, while the charge carrier lifetimes obtained from
the decay traces of TPV measurements (Figure 3f) were 1.59 and 1.83 \selectlanguage{greek}μ\selectlanguage{english}s
for \textbf{Tz-H} - and \textbf{Tz-Cl} -based devices, respectively. The
shorter charge extraction time can be attributed to the higher electron
mobility, and the relatively longer lifetime of free carriers at
open-circuit voltage may indicate less recombination in the
\textbf{Tz-Cl} -based device.

Film morphology

To evaluate the miscibility between the two NFREAs and PM6,
Flory-Huggins interaction parameters (\selectlanguage{greek}\emph{χ} \selectlanguage{english}) were estimated by using
contact angle measurements. The contact angles of two liquids (deionized
water and ethylene glycol) on the neat PM6, \textbf{Tz-H} ,
and\textbf{Tz-Cl} films were investigated (Figure 4a). The surface
tensions (\selectlanguage{greek}\emph{γ} \selectlanguage{english}) of PM6, \textbf{Tz-H} , and \textbf{Tz-Cl} were
calculated to be 19.75, 26.02, and 23.90 mN m\textsuperscript{-1},
respectively (Table S4). According to the empirical
equation\(\chi\ =\ K(\sqrt{\gamma_{D}}-\sqrt{\gamma_{A}})^{2}\), where\emph{K} is a constant, the \selectlanguage{greek}\emph{χ}
\selectlanguage{english}\textsubscript{PM6:\textbf{Tz-H}} and \selectlanguage{greek}\emph{χ}
\selectlanguage{english}\textsubscript{PM6:\textbf{Tz-Cl}} were 0.43 and 0.19\emph{K} ,
respectively, indicating a better D/A miscibility for the
PM6:\textbf{Tz-Cl} blend film.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image6/image6}

\end{center}
\end{figure}

\textbf{Figure 4} (a) Water and ethylene glycol (EG) contact angles of
the neat PM6, \textbf{Tz-H} , and \textbf{Tz-Cl} surfaces. (b) GIWAXS
patterns of PM6:\textbf{Tz-H} and PM6:\textbf{Tz-Cl} blend films and (c)
the corresponding scattering profiles in the out-of-plane (solid line)
and in-plane (dashed line) directions.

The bulk morphologies of blend films were investigated by transmission
electron microscopy (TEM). It is obvious that the
PM6:\textbf{Tz-Cl}blend possessed a smaller domain size and nano-scale
phase separation (Figure S3), which is well consistent with the results
of surface energy. GIWAXS measurements were further utilized to
investigate the morphological feature of the two blend films. As shown
in Figure 4b, face-on and edge-on crystallites coexisted in the
PM6:\textbf{Tz-H}blend film, which is similar to the neat \textbf{Tz-H}
film. Compared with the bimodal texture of the PM6:\textbf{Tz-H} blend
film, the PM6:\textbf{Tz-Cl} blend film exhibited predominant face-on
orientation, which is beneficial to the charge transport in vertical
direction (Figure 4c). As discussed above, these morphological features
indicated that the \textbf{Tz-Cl} -based blend film exhibited a more
favorable morphology, which might be a crucial reason for achieving
better photovoltaic performance.

Conclusions

In conclusion, the electron-deficient units, thiazole and
4-chlorothiazole, were employed to construct two NFREAs, \textbf{Tz-H}
and \textbf{Tz-Cl} , respectively. Compared with\textbf{Tz-H} ,
\textbf{Tz-Cl} possessed a highly-planar backbone, ascribed to the
simultaneous incorporation of S\selectlanguage{ngerman}···N and S···Cl NoCLs. The \textbf{Tz-Cl}
-based device delivered a PCE of 11.10\%, much higher than the
\textbf{Tz-H} -based control device (6.41\%), mainly due to more
efficient exciton dissociation, better and more balanced carrier
mobility, less charge recombination, and more favorable morphology.
Thus, this work provides an effective strategy for designing
high-planarity and low-cost NFREAs via the incorporation of multiple
NoCLs.

Supporting Information

The supporting information for this article is available on the WWW
under https://doi.org/10.1002/cjoc.2021xxxxx.

Acknowledgement

Z. Han and C. Li contributed equally to this work. The authors
acknowledge the financial support from the National Natural Science
Foundation of China (51925306, 52103352, and 52120105006), National Key
R\&D Program of China (2018FYA 0305800), Key Research Program of Chinese
Academy of Sciences (XDPB08-2), the Strategic Priority Research Program
of Chinese Academy of Sciences (XDB28000000), the Youth Innovation
Promotion Association of Chinese Academy of Sciences (2022165), and the
Fundamental Research Funds for the Central Universities. DFT results
described in this report were obtained from the National Supercomputing
Center in Shenzhen (Shenzhen Cloud Computing Center).

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\begin{longtable}[]{@{}l@{}}
\toprule
Manuscript received: XXXX, 2022 Manuscript revised: XXXX, 2022
Manuscript accepted: XXXX, 2022 Accepted manuscript online: XXXX, 2022
Version of record online: XXXX, 2022\tabularnewline
\bottomrule
\end{longtable}

\textbf{Entry for the Table of Contents}\selectlanguage{english}
\begin{longtable}[]{@{}l@{}}
\toprule
\textbf{The Combination of S[?]N and S[?]Cl Noncovalently Conformational
Locks for Constructing High-Planarity and Low-Cost Nonfused-Ring
Electron Acceptors} Ziyang Han, Congqi Li, Xiaobin Gu, Xiao Han, Sixuan
Wang, Yanan Wei, Jinhua Gao, Zhixiang Wei, Yunhao Cai, Xin Zhang* and
Hui Huang* \emph{Chin. J. Chem.} \textbf{2022}, \emph{40}, XXX---XXX.
\textbf{DOI: 10.1002/cjoc.202200XXX}\tabularnewline
Two A-D-A'-D-A type nonfused-ring electron acceptors (NFREAs)
\textbf{Tz-H} and \textbf{Tz-Cl} were designed and synthesized based on
thiazole and 4-chlorothiazole, respectively. Compared with
\textbf{Tz-H}, \textbf{Tz-Cl} possesses a concise synthetic route and
highly planar backbone. Thus, \textbf{Tz-Cl}-based organic solar cell
shows a considerable power conversion efficiency of 11.10\%,
demonstrating the great potential of S[?]N and S[?]Cl noncovalently
conformational locks in achieving low-cost and high-performance
NFREAs.\tabularnewline
\bottomrule
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