PROGRESS REPORT
Organic Cocrystals
Cocrystal Engineering: A Collaborative Strategy toward
Functional Materials
Lingjie Sun, Yu Wang, Fangxu Yang, Xiaotao Zhang,* and Wenping Hu*
Cocrystal engineering with a noncovalent assembly feature by simple
constituent units has inspired great interest and has emerged as an efficient
and versatile route to construct functional materials, especially for the
fabrication of novel and multifunctional materials, due to the collaborative
strategy in the distinct constituent units. Meanwhile, the precise crystal
architectures of organic cocrystals, with long-range order as well as free
defects, offer the opportunity to unveil the structure–property and charge-
transfer–property relationships, which are beneficial to provide some
general rules in rational design and choice of functional materials. In this
regard, an overview of organic cocrystals in terms of assembly, containing
the intermolecular interactions and growth methods, two functionality-
related factors including packing structure and charge-transfer nature, and
those advanced and novel functionalities, is presented. An outlook of future
research directions and challenges for organic cocrystal is also provided.
1. Introduction
Organic functional materials are indispensable for device devel-
opment with the advantages of solution-process capability, low-
temperature processability, light weight, and flexibility, which
are widely applied in the fields of organic photovoltaics (OPVs),
organic light-emitting diodes (OLEDs), organic field-effect tran-
sistors (OFETs), photodetectors, and lasers, etc.[1–5] In particular,
organic single-crystal materials with features of nongrain
boundaries, minimized impurities, and free defects are essential
for enhanced device performance with respect to their corre-
sponding polycrystalline or amorphous thin films.[6–8] Recently,
organic cocrystals have gained considerable attention and
emerged as a promising research interest to construct functional
L. Sun, Dr. Y. Wang, Dr. F. Yang, Dr. X. Zhang, Prof. W. Hu
Tianjin Key Laboratory of Molecular Optoelectronic Sciences
Department of Chemistry
School of Sciences
Tianjin University & Collaborative Innovation Center of Chemical Science
and Engineering
Tianjin 300072, China
E-mail: zhangxt@tju.edu.cn; huwp@tju.edu.cn
Prof. W. Hu
Beijing National Laboratory for Molecular Sciences
Key Laboratory of Organic Solids Institute of Chemistry
Chinese Academy of Sciences
Beijing 100190, China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201902328.
DOI: 10.1002/adma.201902328
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materials,[9–12] which are crystalline single-
phase materials composed of two or
more different compounds generally in
a stoichiometric ratio,[13] providing a plat-
form for unveiling the structure–property
relationships at a molecular level.[14] The
building blocks are assembled via non­
covalent interactions, offering the opportu­
nity to achieve noncovalent synthesis of
functional molecules.[15] Compared with
the traditional covalent synthesis, cocrystal
engineering offers numerous advantages,
including: 1) avoiding complicated syn-
thesis procedures, and cocrystal assem-
blies have been successfully fabricated by
the vapor methods and solution-processing
methods in a facile and low-cost way;
2) manipulating intermolecular inter-
actions through selecting suitable con-
formers from a plentiful supply of raw
materials, resulting in tunable structures, morphologies, and
sizes; 3) achieving rare and multifunctional properties through
a collaborative strategy in distinct constituent units, which are
difficult to realize for individual components.[16–18]
Cocrystal engineering began to draw much attention
since the exploration of the metal conductive tetrathiafulva-
lene–7,7,8,8-tetracyanoquinodimethane (TTF-TCNQ) cocrys-
tals in 1973.[19] The peculiar conductivity in organic materials
makes it possible for cocrystals to serve as organic electrodes,
which can effectively lower the contact resistance and further
improve device performance. Encouraged by this, cocrystals
can serve as a breakthrough and provide an opportunity to dis-
cover novel physicochemical properties, which are far beyond
the performance of single materials. In this respect, dielectric
response[20] and nonlinear optics[21,22] are also realized through
rational design of each component, which is absent in their
constitute components. Even more, the bottom-up supramo-
lecular assembly provides the opportunity to equip them with
the individual properties of the donor or acceptor to create
multifunctional materials.[23] Typically, ambipolar charge trans-
port can be generated by coassembling p-type semiconductors
and n-type ones, and the charge-carrier mobility is now up to
1.57 cm2 V−1 s−1 for holes and 0.47 cm2 V−1 s−1 for electrons.[24]
To date, these exciting results accelerate the investigations of
organic functional cocrystals, such as room-temperature ferro-
electricity,[25–27] optical waveguide properties,[28,29] pure organic
room-temperature phosphorescent properties,[30–32] stimulus-
response (e.g., mechanical stress,[33,34] heat,[35,36] or solvent[37])
characteristics, photovoltaics,[38] and near-infrared photo-
thermal (PT) conversion and imaging,[39] etc.
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Although this field is fascinating, the development of func-

tional cocrystals is actually slowly progressing, which may be Lingjie Sun received her
attributed to a structural mismatch in distinct constituent M.Sc. degree from the
compounds, the ambiguous mechanism of cocrystallization, Department of Chemistry,
and overall properties may alter in unpredictable ways.[40–42] School of Science,
In order to help readers to understand this promising field, Tianjin University and the
a timely and insightful review of organic cocrystals toward Collaborative Innovation
functional materials is present, which is expected to open up Center of Chemical Science
a new design principle of functional materials for practical and Engineering (Tianjin) in
applications. As shown in Figure  1, we first introduce several 2017. Since September 2017,
considerations for fabricating organic donor–acceptor cocrys- she has been a Ph.D. student
tals, including intermolecular interactions for molecular rec- in the same department
ognition and coassembly as the internal driving force and (supervisor: Prof. Wenping
growth methods of organic cocrystals as the external affecting Hu). Her interests are in the design, characterization, and
factors, aimed at providing a general guideline for the growth optoelectronic properties of organic cocrystals.
of high-quality, high-performance organic functional cocrystals.
Moreover, the molecular arrangements and charge-transfer
interactions (CT) are essential for the functionalities of organic
cocrystals; thus, the structure/CT–property relationship are Yu Wang is a Ph.D. candidate
fully discussed and summarized. Then, we demonstrate the (supervisor: Prof. Wenping
advanced and emerging functionalities of organic cocrystals, Hu) in the Department of
including optical functionalities, electrical functionalities, and Chemistry, School of Science,
innovative functionalities. Finally, encountered challenges Tianjin University and at
and future opportunities for further improvement are also the Collaborative Innovation
organized. Center of Chemical Science
and Engineering (Tianjin).
In 2014, she received her
B.S. degree from Tianjin
2. Rational Design and Controllable Preparation University. Her research
of Organic Cocrystals focuses on organic
2.1. Intermolecular Interactions for Effective Molecular optoelectronic cocrystals including material science,
Recognition and Coassembly assembly technology, and their advanced optoelectronic
applications.
Over the past decades, exploring the fundamental princi-
ples of molecular recognition has attracted obvious interest Wenping Hu is a professor at
(Scheme 1). The cocrystallization of organics is fundamentally Tianjin University and ICCAS.
related to the composition of individual molecules, wherein He received his Ph.D. degree
the molecular size, shape, and steric factors, as well as the from ICCAS in 1999. He then
intermolecular interactions are of paramount importance for joined Osaka University as a
regulating the arrangements of cocrystals.[15] The synergistic research fellow of the Japan
effect of those noncovalent-bonding interactions between Society for the Promotion
homomeric and heteromeric molecules governs recognition of Sciences and Stuttgart
and assembly processes. Cocrystals have a more stabilizing University as an Alexander
lattice energy than the sum of coformers.[43] Consequently, von Humboldt fellow. In
with strong heteromeric molecular interactions, cocrystalliza- 2003, he worked for Nippon
tion would take place in a mixed molecular system rather than Telephone and Telegraph,
the crystallization of individual coformers. Also, the balance and then returned to ICCAS and was promoted to a
of those interactions plays a key role in directing the final full professor. In 2013, he joined Tianjin University. His
cocrystal packing structure and morphology, and hence its research focuses on molecular electronics.
physiochemical properties.[44] In order to guide future rational
design, it is essential to explore the relationship between the
inherent driving force and cocrystallization process, which CT interaction usually takes place in systems composed of
requires in-depth understanding of the coassembly driving charge-donating and charge-accepting molecules, named donor
interactions nature (e.g., strength and directionality). In (D) and acceptor (A), respectively. Its strength is characterized by
organic cocrystals, typical heteromeric intermolecular inter- the degree of charge transfer (DCT), depending on the donor’s
actions are represented for charge-transfer interactions, ionization potential (IP), the electron affinity of the acceptor
π–π interactions, hydrogen bonds, and halogen bonds.[45] (EA), and the electrostatic Coulomb interactions in cocrystals.[46]
Their significance in cocrystal engineering can hardly be With a large DCT, a cocrystal prefers to display a strong ionic
underestimated. character and follows a segregated-stacking mode to stabilize

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Figure 1. An overview addressing the key points of organic cocrystals toward functional materials by collaborative strategies, including organic
assembly, the structure/CT–property relationship, and their optical, electrical, and innovative functionalities.

the ionic behavior. In contrast, a smaller DCT (DCT < 0.5)
results in a neutral/quasineutral cocrystal in general.[47] In fact,
most functional cocrystals are neutral/quasineutral and dis-
play CT features, wherein charge transfer occurs coupled with
strong interactions such as π–π interactions, hydrogen bonds,
and halogen bonds between heteromeric molecules.[9] For
instance, cocrystals composed of strong electron acceptors, such
as 7,7,8,8-tetracyanoquinodimethane,[48–50] tetracyanobenzene
(TCNB),[34,51] and C60,[52–54] generally display π–electron delo-
calization from the donor to the acceptor, that is, intermolecular
charge transfer. For example, the cocrystal composed of 4-sty-
rylpyridine (Spe, donor) and TCNB (acceptor) follows a mixed-
stack structure, wherein Spe and TCNB stack face-to-face alter-
natively with strong intermolecular interactions (Figure  2a).[55]
Meanwhile, its large redshifted absorption peak, strong radical
signal in electron spin resonance (ESR) spectra, and significant
shifts in solid-state 13C NMR reveal the existence of a charge-
transfer process from Spe to TCNB. Moreover, attributed to the
directional nature and complementarities of CT interaction,[56]
those cocrystals tend to display a 1D morphology. However,
rational design of intermolecular interactions would support
the effective regulation of cocrystal morphology. For instance,
the expansion of hydrogen bonds would restrict the driving role
of the CT interaction and result in a targeted 2D morphology.
The Spe–TCNB cocrystal discussed above exhibits a 1D ribbon-
like morphology, wherein Spe includes one benzene ring and
one pyridine ring. Compared to Spe, 1,2-di(4-pyridyl)ethylene
(Bpe) has a similar structure but contains two pyridine rings.
In Bpe–TCNB cocrystal,[14] the increase number of N atoms also
increases the intermolecular –CH···N– interactions, and that
induces molecular aggregation and expansion into a layered
structure, making BTC a unique 2D parallelogram-like shape
rather than traditional 1D wires or rods (Figure 2b).
In terms of conjugated cocrystals, the π–π interaction plays
an essential role in coassembly processes. The design strategies
are sorted into two kinds: one is to select a conjugated donor
and acceptor with efficient π–electron donating and accepting
ability, respectively, such as the CT pyrene–TCNQ cocrystal,[57]
anthracene–TCNB cocrystal,[58] ZnTPP–C70 cocrystal,[59] and so
on. The other is to choose a donor and acceptor with similar
molecular skeleton or isometric structure.[37] For instance,
the arene–perfluoroarene (AP) interaction, which repre-
sents the interaction between nonfluorinated and fluorinated
π-conjugated molecules, makes donors and acceptors prone
to coassemble with a mixed-stacking mode in the solid state,
even when the CT characters are absent. Hu’s group designed

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Scheme 1.  The donors and acceptors of organic cocrystals discussed herein.
an AP cocrystal composed of pyrene and octafluoronaph-
thalene (OFN), which displayed a uniform 1D morphology
(Figure 2c).[60] Notably, the absorption spectrum of pyrene–
OFN cocrystal tended to be the sum of two coformers, without
a remarkable redshift CT absorption peak, demonstrating the
absence of a CT character. The π–π interaction between planar
molecules provides an arrangement diversity of conjugated
molecules in the cocrystal, which correlates to various factors
like the interaction type (i.e., π···π, CH···π interactions)
and packing motifs (i.e., herringbone, cofacial herringbone,
face-to-face, brickwork).[6] This reduces the degree of structure
predictability. In contrast, the concave–convex π–π interaction
exhibits stronger directionality due to its curved characteristic.
Therefore, the stacking structure and morphology are more
controllable and predictable. Hu’s group has developed it as an
efficient 1D assembly strategy (Figure 2d).[61] They chose a bowl-
shaped molecule corannulene to restrain the growth direction
of C60. As expected, the intermolecular concave–convex π–π
interaction between corannulene and C60 is the strongest com-
pared to other intermolecular interactions. Hence, the donor
and acceptor molecules stack alternatively and lead to a targeted
1D morphology. Notably, the geometric effect plays a crucial
role in such an assembly process as the molecular recognition
requires curvature matching of two molecules.
The hydrogen bond, the primary key for molecular recogni-
tion, is a reliable directional interaction in cocrystal systems.[62]
A typical hydrogen bond is illustrated as X–H···Y–Z, where
X–H represents the proton donor and X has a larger electron-
egativity than H. The proton acceptor is an electron-rich region
(i.e., a lone pair of Y, π-bonded pair of Y–Z) and it may be an
atom, an anion, a fragment, or a molecule.[63] Hence, the larger
electronegativity of X, the stronger hydrogen bond, while its
angle X–H···Y tends to be linear. With marked directionality
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and strength, the hydrogen bond is the foundation of efficient
supramolecular construction.[64–66] It not only favors molecular
packing structure prediction with a rational degree of accuracy,
but also has been widely applied as a cement to build robust 1-,
2-, or 3D cocrystal networks. A recent example is the pyrom-
ellitic diimide–based cocrystal designed with a lock-arm supra-
molecular ordering (LASO) strategy.[67] With the cooperation
of the CT interaction and hydrogen bonds, the molecules are
locked by a large-scale network in a tightly packing mode, and
that makes the cocrystal mechanically robust. More importantly,
the cocrystals designed by this strategy could undergo room-
temperature ferroelectric polarization switching (Figure 2e)[68]
and realize two-axes ferroelectric polarization (Figure 2f),[69]
which are unusual among organics.
The halogen bond is another versatile element for reasonable
design of organic cocrystals, which stands for the electrostatic
interaction between an electron donor (halogen-bond acceptor)
and a polarized halogen atom (I, Br, Cl, and sometimes F)
that is bonded with electron-withdrawing groups (halogen-
bond donor).[70] The bond strength is shown to be energeti-
cally competitive and sometimes stronger than the hydrogen
bond, which increases with the increase size of the halogen
donor atom, that is, F < Cl < Br < I. With superior strength and
directionality, the halogen bond would also promote the con-
struction of robust and reproducible cocrystal structures.[71,72]
Extensive functional groups could engage in the recognition
and coassembly processes, wherein plenty of electron-rich
species have been explored as halogen-bond acceptors, i.e., π
systems, N-, S-, or Se-based acceptors.[73–75] This would be in
favor of further understanding of the intermolecular interac-
tions and uncovering their relationships with cocrystal packing
structures. Recently, Bpe was explored as a N-based halogen
acceptor, which can recognize two similar halogen donors
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Figure 2.  The role of intermolecular interactions on the coassembly processes. Charge-transfer interaction: a) A confocal laser scanning microscopy
(CLSM) image of the Spe–TCNB cocrystal and the corresponding molecular packing structures. Reproduced with permission.[55] Copyright 2017,
Wiley-VCH. b) A CLSM image of the Bpe–TCNB cocrystal and the corresponding molecular packing structures. Reproduced with permission.[14]
Copyright 2015, Wiley-VCH. π–π interaction: c) A CLSM image of the pyrene–OFN cocrystal and the corresponding molecular packing structures.
Reproduced with permission.[60] Copyright 2017, Wiley-VCH. d) An optical microscopy image of corannulene–C60 cocrystal and the corresponding
molecular packing structures. Reproduced with permission.[61] Copyright 2016, RSC Publishing. Hydrogen bonds: e,f) A pyromellitic diimide–based
cocrystal with room-temperature ferroelectric polarization (e), and two-axes ferroelectric polarization (f). e) Reproduced with permission.[68] Copyright
2012, Nature Publishing Group. f) Reproduced with permission.[69] Copyright 2017, American Chemical Society. Halogen bonds: g,h) CLSM images
of Bpe–IFB cocrystal and the corresponding molecular packing structures (g) and of Bpe–F4DIB cocrystal and the corresponding molecular packing
structures (h). g,h) Reproduced with permission.[76] Copyright 2015, American Chemical Society. Bpe-TCNB, Refcode 1405953 from CSD; pyrene-OFN,
Refcode 157249 from CSD; corannulene-C60, Refcode 864755 from CSD; Bpe-IFB, Refcode 293753 from CSD; Bpe-F4DIB, Refcode 161324 from CSD.
Note: The Refcode number refers to the crystal number in the Cambridge Crystallographic Data Centre (CCDC).

1,3,5-trifluoro-2,4,6-triiodobenzene (IFB) and 1,4-diiodote-
trafluorobenzene (F4DIB) with a 1:1 stoichiometry ratio.[76]
The Bpe–IFB cocrystal displays a segregated-stacking mode,
while two types of intermolecular N···I halogen bonds con-
nect the adjacent Bpe and IFB columns, stretching along dis-
tinct directions. Therefore, it restrains the expansion of inter­
molecular halogen bonds along one direction. At the same time,
the π–π interaction between Bpe molecules plays a dominant
role and triggers its 1D growth (Figure 2g). In sharp contrast,
Bpe–F4DIB cocrystal forms a mixed-stacking structure. The
intermolecular N···I halogen bonds form a linear Bpe–F4DIB
molecular chain. Combined with heteromeric intermolecular
C–F···H interactions, they together contribute to the expan-
sion of the 2D molecular plane and its unusual 2D morphology
(Figure 2h).
To date, the exploration of the relationship between inter-
molecular interactions and the cocrystal coassembly processes
has made great progress, which makes it possible to guide

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the selection of donor/acceptor molecules and the prediction
of molecular coassembly processes to some extent. However,
the diversity of those noncovalent interactions and molecular
chemical structures makes it a long-term task. Therefore, more
in-depth studies based on a series of compounds and processes
should be conducted for a more general strategy. Moreover,
the intermolecular interaction would greatly affect the packing
structure, which closely correlates to the electronic conjugation,
and hence the functional properties of cocrystals. Therefore,
exploring the relationship between intermolecular interactions,
packing structures, and functionalities is also of paramount
importance, which would not only promote the accurate pre-
diction, but also be in favor of the construction of a material-
design strategy.
2.2. Controllable Preparation Strategies for Organic Cocrystals
Organic cocrystals are ordered solids assembled by intermo-
lecular interactions, but cocrystallization only occurs between
some certain molecules.[77,78] That is, not all molecules can
recognize and assemble to form a cocrystal. Therefore, how
to choose the constituent molecules, how to promote an effec-
tive coassembly process to prepare a new cocrystal, is one of
the primary problems. Apart from pondering the importance of
intermolecular interactions in multiple molecules, the applied
methods as the external conditions for effective cocrystalli-
zation should also be taken in consideration. This is because
the growth methods will affect the morphology and packing
mode of the crystal, and further affect the performance of the
device.[79,80] Thus, choosing a suitable growth method is critical
to achieving desired crystal for different needs. Similar to the
crystal growth of monomolecular materials, the vapor tech-
nique and solution-processing method are popular in the coas-
sembly process of cocrystals as well. In the following section,
therefore, we will introduce the cocrystal preparation methods,
as well as their own advantages, drawbacks, and applicable con-
ditions in the growth process to obtain high-quality cocrystals
for advanced functional applications.
The vapor method refers to the sublimation process of a
material from solid to gas that will occur at low pressure and
temperature (the temperature is normally lower than the
melting point and the decomposition point of the materials,
and the pressure is less than one atmosphere), and then the
sublimed donor and acceptor molecules recognize and coas-
semble mutually, accompanied by a recrystallization in a cooler
zone to form the final products.[81,82] This method can be used
to prepare cocrystals with high-quality, thin and clear shape,
and high chemical purity, which can be easily amenable for
constructing the micro-/nanocrystals used in high-performance
optoelectronic devices.[83] Moreover, this method is suitable for
materials with low solubility, expanding the diversity of cocrystal
preparation methods.[84] To be sure, the vapor method is essen-
tial for cocrystal growth, although the successful examples of
cocrystals by the vapor technique are rare due to the difficulties
in controlling the final products. Among the various vapor tech-
niques, physical vapor transport (PVT) has been widely used
for organic semiconductor single crystals since Kloc’s group
pioneered the first demonstration of crystal growth in 1990s.[85]
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Many factors,[86–88] such as sublimation rate for supersatura-
tion, vapor pressure, the stoichiometric ratio between donor
and acceptor, etc., are crucial for cocrystal growth in PVT, so we
will next explain in detail how to grow cocrystals by using PVT.
Due to the existence of two or more components, typical PVT
processes have two types according to the sublimation points
of the constituent compounds, as shown in Figure  3a. One is
that the donor and acceptor powders can be mixed together
in a suitable position of a quartz tube, which holds for the
donor and acceptor materials with similar sublimation points
(Figure 3a-i).[89–91] For example, the diphenyldipyrollopyridine–
naphthalenetetracarboxydiimides cocrystals, also called DP–
P2P:NDI, can be prepared by coevaporation of a ground
mixture of the components in vacuum. Powder X-ray diffrac-
tion (XRD) shows an identical diffraction pattern for solution
and vapor-grown cocrystals and confirms the absence of the
crystalline phases of the individual components, indicating
the effectiveness of gas-phase growth to grow high-quality
cocrystals.[92] Meanwhile, the source materials of cocrystals
can originate from well-grown cocrystals from solution but
not those mixtures of separate donor and acceptor molecules,
which effectively improves the yield and quality of cocrystals.[93]
On the other hand, the second type of PVT model is used
for systems that have significantly different sublimation tem-
peratures.[94] The starting materials of the donor and acceptor
are placed in different positions on one side of a furnace such
that their sublimation rates will be comparable (Figure 3a-ii).
The temperatures of the source materials play an important
role in the process of the cocrystal growth, which can not only
promote the materials being sublimated but also form a tem-
perature gradient to transport the sublimated molecules to the
cooler zones. Thus, the sublimation rate can be regulated by
the temperatures of the source materials, leading to diverse
vapor pressure and temperature gradients of the sublimated
materials, which will cause selective growth of the sublimated
materials. As in the case of perylene–TCNQ cocrystals, the
stoichiometric ratios (e.g., 1:1, 2:1, 3:1) are obtained by con-
trolling the sublimation temperature of perylene at 180, 200,
and 220 °C. Unfortunately, it seems impossible to control the
formation of a compound precisely in this open system with
a flowing carrier gas, which involuntarily turns to distinguish
from each other by the colors and shapes of the final products.
As shown in Figure 3b, a typical mixture of phases grown in an
open PVT system is obtained, and the dark-colored crystals of
the binary compounds are easily distinguished from the yellow
crystals of monomolecular TCNQ or perylene. In addition, the
P1T1 crystals are needle-like shapes, which are visually distin-
guished from those P2T1 and P3T1 crystals with platelet-like
shapes.[95] Moreover, using the single crystals of individual
components rather than powder samples of that are favorable
for growing large-size cocrystals.[96,97] Jiang’s group demon-
strated that single-crystal samples as the source materials, due
to their smaller surface area, could afford a lower sublimation
rate than that of powder samples, while a larger temperature
gradient offers the opportunity for transporting the sublimated
molecules to cocrystallize on the prepared seeds.[96] Thus,
centimeter-long crystals of novel perylene–F1TCNQ, perylene–
F2TCNQ, and perylene–F4TCNQ cocrystals were obtained from
the gas phase (Figure 3c), which are convenient for detailed
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Figure 3.  a) The PVT method for organic cocrystal growth: i) this system is suitable for the donor and acceptor materials with similar sublimation
points; ii) this system is suitable for the donor and acceptor materials with different sublimation points. b) A typical mixture of phases grown in an
open PVT system with flowing argon gas. b) Reproduced with permission.[95] Copyright 2014, American Chemical Society. c) Perylene–F4TCNQ charge-
transfer-compound single crystals. Reproduced with permission.[96] Copyright 2016, RSC Publishing. d) Solution-processing methods for the cocrystal
growth: i) method of solvent evaporation; ii) gas-phase diffusion method; iii) liquid-phase diffusion method; iv) drop-casting method. e) Schematic
illustration of the formation mechanism of cocrystal. f,g) Optical images of microblock (f) and nanowire (g) crystals on a glass substrate. e–g)
Reproduced with permission.[102] Copyright 2015, Wiley-VCH. h) The corresponding diffraction patterns for DPTTA-based microcrystals. Reproduced
with permission.[24] Copyright 2016, RSC Publishing. i,j) CIF of single-crystal data and XRD pattern of crystals grown on glass by solution drop-casting
of DPDA–IFB-I (i) and DPDA–IFB-II (j). i,j) Reproduced with permission.[101] Copyright 2017, RSC Publishing.

studies of the anisotropy of the physical properties and the
structure–property relationships. The cocrystals based on
vapor phase growth have the characteristics of high quality and
solvent free, so the enrichment and development of vapor-based
methods is favored over PVT. For example, Tao and coworkers
reported an unprecedented vapor-to-melt-to-crystal mechanism
to grow organic single crystals by a microspacing in-air subli-
mation method, avoiding the costly vacuum system and time-
consuming procedures in common PVT.[98] Subsequently, they
successfully prepared organic cocrystals by using this method,

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and the morphology of the cocrystals can be tunable from 1D
needle-like to 2D plate-like on demand.[99]
Compared with the crystallization process in the vapor
process, the solution-processing method can serve as a
more effective way for the synthesis of cocrystals due to its
facile preparation, low cost, and good controllability.[58,100] In
the dilute solution state, the molecules move freely; however,
when the solution reaches saturation or supersaturation, the
donor and acceptor molecules are mutually recognized, coas-
sembled, nucleated, and crystallized based on their strong
noncovalent bonds. Therefore, the solvent evaporation rate for
saturation or supersaturation is believed to be critical to the
formation of a well-ordered structure. In addition to the use
of a donor–acceptor mixed solution, these methods produce a
cocrystal in a manner similar to the growth of a one-component
crystal from solution.[45] However, due to the complexity of
cocrystals based on two or more components in the liquid state,
many factors in the liquid state may affect the final products.
For example, the type of solvent,[101] the concentration,[102] and
the temperature[52] can cause the solubility to be different;
at the same time, the strengths of the intermolecular interac-
tions between the donors and acceptors may be different in
the selected method, so the growth rate, quality, and size of the
formed cocrystals are influenced.[103] In this regard, we will next
introduce some of the most frequently employed methods to
produce cocrystals among liquid-phase methods: methods of
solvent evaporation, diffusion methods, and drop casting, aimed
at giving some general guidelines by using those methods.
Specifically, methods of solvent evaporation usually dissolve
a certain ratio of the reactant mixture solution in a bottle, which
is then kept in a dark environment. As the solvent evaporates,
the solute gradually reaches a saturated state in the solution,
and forms a crystal nucleus under the driving of the intermo-
lecular interaction, and then gradually precipitates after several
days (Figure 3d-i).[104] This method normally requires that the
donor and acceptor molecules have similar solubilities in the
same solvent, and highly depends on factors such as solvent,
concentration, temperature, and other external conditions.
For example, Zhu et al. revealed that the donor and acceptor
concentration had an effect on perylene–TCNQ (PxTy) cocrys-
tals (Figure 3e).[102] That is, a high perylene concentration was
favorable for the formation of P3T1 cocrystals with a block-like
parallelogram shape (Figure 3f), while low perylene concentra-
tion facilitated the formation of P1T1 cocrystals with a wire-like
crystal (Figure 3g).
Diffusion methods are divided into the gas-phase diffusion
method and the liquid-phase diffusion method. For the former,
the sample bottle containing the mixture solution of the donor
and acceptor molecules is placed in another large container,
and a low-boiling poor solvent is placed in the container. After
sealing, the external poor solvent is diffused into the sample
bottle through the solvent vapor, thereby lowering the solubility
of the donor–acceptor solution; finally, the cocrystals gradually
precipitate and grow up (Figure 3d-ii). For the latter, the com-
monly used device is an H-shaped tube. The solid powders of
the donor and acceptor are placed in the bottom of the left and
right branches, respectively, and followed by adding the same
solvent slowly to both sides of the tube until it exceeds the
middle horizontal branch; finally, the H-shaped tube is sealed.
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After the molecules dissolve and diffuse, they meet at the hori-
zontal branch, self-assemble and precipitate into cocrystals
(Figure 3d-iii). Those diffusion methods are time-consuming,
which allows molecules to diffuse slowly and give bulk crystals
for X-ray single-crystal structure characterization. Qin et al.
used this H-shaped tube diffusion method for preparing high-
quality large crystals of diphenyltetrathia[22]-annulene[2,1,2,1]
(DPTTA)-based CT cocrystals (Figure 3h).[24]
The drop-casting method is used to prepare micro/nano
cocrystals for exploring the growth orientation and device
applications, and involves dropping several droplets of donor–
acceptor solution onto the substrate directly. After the evapora-
tion, the cocrystals are formed (Figure 3d-iv). For example, two
cocrystal phases of 1,4-di(4′-pyridyl)-1,3-diacetylene (DPDA) and
IFB were obtained by the drop-casting method with different sol-
vents of acetonitrile and methylene chloride.[101] Those micro/
nanostructures have different PXRD patterns but match per-
fectly the calculated lines from the single-crystal data. Further
structural characterization by PXRD suggests that DPDA–IFB-I
grows along the crystallographic b-axis (010), whereas DPDA–
IFB-II grows along the crystallographic c-axis (001) direction
(Figure 3i–j). In summary, the solution-processing methods
involve the use of a solvent, which will inevitably pollute the
external environment, and sometimes the solvent can enter into
the framework of the cocrystals, which will have a great con-
tribution to the photophysical properties of the cocrystal. Nev-
ertheless, the solution-processing methods are indispensable to
grow cocrystals, attributed to the characteristics of simple pro-
cessing; low cost as well as can be appropriate for most soluble
organics. Therefore, developing some environmentally friendly
solvents to grow organic cocrystals is a good choice.
3. Functionality-Related Fundamental Principles
of Organic Cocrystals: Packing Structures and
Charge-Transfer Nature
3.1. Unveiling the Structure–Property Relationship in
Organic Cocrystals
Recently, cocrystal materials have generally exhibited attractive
performance with advanced applications in various fields.[35,105–107]
However, as a new design strategy toward functional materials,
to realize targeted design toward functional cocrystal materials,
it not only requires the coassembly processes to be understood,
but also needs to explore the functionality-related principles.
Indisputably, the functional performance of cocrystals has
a close relationship to diverse factors, such as their coformer
molecules, intermolecular interactions, cocrystal stacking struc-
tures, and so on.[17] Also, the variety of coformer molecules, the
balance of intermolecular interactions, the selection of prepa-
ration methods and conditions, etc., would result in diverse
molecular-packing structures, which are closely related to the
functionality properties of cocrystals attributed to their differ-
ence in electronic conjugation structures.[108–110] Therefore,
there is an urgent demand to reveal the structure–property
relationship in the cocrystal field, which would be beneficial for
the design and synthesis of functional cocrystals. Fortunately,
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Figure 4.  The structure–property relationship in cocrystal system. a–d) Schematic diagrams of typical cocrystal molecular packing modes; and e–h) the
corresponding representative cocrystal structures; i,j) two polymorphs of the DBTTF–TCNQ cocrystal; i,j) Reproduced with permission.[93] Copyright 2016,
Wiley-VCH. k,l) The TPA functionality comparison of the individual component Npe and the corresponding cocrystal Npe–F4DIB. k,l) Reproduced with
permission.[120] Copyright 2016, Wiley-VCH. TTF-TCNQ, Refcode 1275955 from CSD; P1T1, Refcode 1050045 from CSD; P2T1, Refcode 1429735 from
CSD; P3T1, Refcode 1050046 from CSD. Note: The Refcode number refers to the crystal number in the Cambridge Crystallographic Data Centre (CCDC).

the diverse cocrystal packing structures provide a multitude
of opportunities in uncovering the relationship between
molecular-packing structures and their functional properties,
and significant progress has been made over the past decades.
In terms of common 1:1 binary cocrystals, the typical
packing motifs can be divided into segregated-stacking mode
and mixed-stacking mode, as shown in Figure  4a,b. In segre-
gated-stacking systems, the donor and acceptor molecules pack
separately in adjacent columns (-D-D-D-D- and -A-A-A-A-), and
a classic example is the TTF–TCNQ CT salt (Figure 4e).[111]
Meanwhile, in mixed-stacking systems, donor and acceptor
molecules pack alternately along their face-to-face stacking direc-
tion (-D-A-D-A-), which is represented for the tetracene–TCNQ
cocrystal. With a 2:1 stoichiometry, the extra donor may form
another additional column in segregated-stacking mode (-D-D-
D-D-, -A-A-A-A-, and -D-D-D-D-),[92] insert in the mixed-stacking
column (-A-D-D-A-D-D-A-D-D-),[112] or form another additional
column in the mixed-stacking mode (-D-A-D-A-D-A-D-A and
-D-D-D-D-, Figure 4c). Meanhile, for a 3:1 stoichiometry, it
turns to display one stacking mode (Figure 4d): two additional
donors insert in the mixed-stacking column and form another
additional column, respectively (-A-D-D-A-D-D-A-D-D- and
-D-D-D-). Taking the perylene–TCNQ system as an example,
the donor–acceptor ratio can vary from 1:1, 2:1, to 3:1, which
are called P1T1, P2T1, and P3T1, respectively (Figure 4f–h).[95]
P1T1 exhibits a mixed-stacking mode, while P2T1 consists of
mixed-stacking column with an additional perylene inserted
between adjacent columns and forms an additional column. In
P3T1, compared to P2T1, the additional perylene is inserted in
the mixed-stacking column.
The polymorph phenomenon, which refers to cocrys-
tals composed of the same donor and acceptor but following
different arrangements in the solid crystalline phase, provides us
an ideal platform for revealing the interplay between structure
and property, due to the fact that the difference in packing struc-
ture would yield different electronic conjugations and hence
discernible physicochemical properties, such as morphology,
melting point, and especially for their fascinating optoelectronic

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properties.[10] Taking the conductivity as an example, to achieve
room-temperature metallic conductivity, segregated-stacking
is indispensable rather than mixed-stacking in the over-
whelming majority of cases.[113] An impressive example is the
TMTSF–TCNQ cocrystal.[114,115] With a 1:1 stoichiometry, it may
undergo either the segregated-stacking or the mixed-stacking
mode, and that leads to their distinct conductivity, wherein the
segregated cocrystal is a black metal while the mixed one is a
red semiconductor. Moreover, the charge-transport behaviors
are greatly dependent on the molecular arrangements, which
govern the coupling degree between constituent molecules
and the hybrid band structure. Therefore, a small change of
molecular arrangement would result in a significant variation
of electrical properties. A remarkable example is the diben-
zotetrathiafulvalene (DBTTF)–TCNQ cocrystal.[93] The two
polymorphs display different unit-cell parameters and altered
molecular arrangements, but both follow mixed-stacking
modes (Figure 4i,j). However, their properties are signifi-
cantly distinct. The rectangular-shaped α-phase DBTTF–TCNQ
cocrystal exhibits superior electron transport, while the ellip-
tical-like β phase displays hole-dominant transport, attributed
to the change of band structure and a different charge-injection
barrier. Since it remains challenging to realize controlled prepa-
ration of polymorphs, molecular rearrangement in cocrystal
systems with phase-transition processes serves as another
shortcut to uncover the structure–property relationship.[116–118]
For instance, Tian’s group explored a piezochromic lumi-
nescent cocrystal composed of 1,4-bis-p-cyanostyrylbenzene
(CNDSB) and TCNB.[34] Under grinding, the shear force would
induce an opposite sliding direction between neighboring
molecular columns, making the segregated-stacking mode
turn into mixed-stacking, weakening the π–π interaction and
CT interaction. Consequently, the cocrystal system displayed a
significant hypochromatic shifted emission. In sharp contrast,
while under hydrostatic pressure, the pressure leads to a tighter
packing, enhancing the π–π interaction and CT interaction,
which results in a bathochromatic shifted emission.
In addition, with a fixed donor and acceptor, the variation
of stoichiometry ratio of the donor and the acceptor, named
stoichiomorphism,[48] would also induce dramatic changes in
the molecular arrangements, and hence their functionality.
Taking the perylene–TCNQ system as an example,[95] with an
increase of donor–acceptor proportion, the hole-transport capa-
bility increases while the electron-transport ability decreases.
As a result, P1T1 is an n-type semiconductor, P2T1 exhibits
ambipolar charge-transport behavior, while P3T1 shows a hole-
dominant transport.
In spite of the polymorph and stoichiomorphism, the com-
parison with cocrystals composed of only one same individual
component (donor or acceptor) would also provide a shortcut
to reveal the structure–property relationship and be in favor
of the construction of fundamental theories. For instance, it
is widely accepted that the spectroscopic behaviors of organic
solid materials are dependent on their molecular arrange-
ments. Therefore, cocrystallization is a potential candidate
for tunable optical properties. Also, it has been discovered
that the optical behaviors of individual components may be
altered in cocrystal systems through synergistic effects.[65,119]
Guldi’s group[59] has developed a series of cocrystal nanosheets,
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wherein C70 and (metallo)porphyrins act as acceptor and
donors, respectively. Notably, after cocrystallization, the
localized (metallo)prophyrins fluorescence undergoes a quan-
titative quenching. That is attributed to the significant charge-
transfer characteristics in the cocrystal system leading to a
large charge-density redistribution. In addition, cocrystal engi-
neering may also retain the original properties of the cofor-
mers. 4-(1-Naphthylvinyl)pyridine (Npe) is a material with
efficient two-photon absorption (TPA) properties (Figure 4k).
The halogen-bond cocrystal composed of Npe and F4DIB also
displays remarkable TPA properties (Figure 4l), on account
of the donor–acceptor halogen bonds acting as a bridge to
expand the D–π–A configuration. Moreover, the Spe–F4DIB
cocrystal[120] displays almost identical absorption and emission
spectra with analogous excited-state dynamic processes to that
of Spe crystal. A similar phenomenon has also been observed
in the Bpe–F4DIB cocrystal system,[76] which displays similar
absorption and emission spectra compared to individual Bpe
molecules. These unusual phenomena suggest that cocrystal
engineering remains to be a fascinating field, and the revealing
insights into these would critically pave the development of
cocrystal theoretical physics, which would further guide the
rational cocrystal material design.
The development of experimental and theoretical research
has not only deepened the understanding in packing–perfor-
mance relationships in cocrystal systems, but also provides
guidance toward high-performance functional cocrystals in
fascinating optoelectric applications. However, further in-
depth studies should be conducted to achieve rational design,
including: 1) the controlled design and preparation of poly-
morphs, different stoichiometry as well as similar donor–
acceptor cocrystals to enrich the research systems, 2) the
exploration and comparison of similar cocrystal systems with
diverse functionalities to provide more comprehensive research,
and 3) the construction of structure-related theoretical physics
to promote targeted design.
3.2. Revealing the CT–Property Relationship in
Organic Cocrystals
The CT interactions are manipulated as a powerful driving
force to assemble the constituent units into aligned structures
in the solid state, resulting in cocrystal fabrication with the
features of high-quality and regular morphology.[121] Moreover,
the CT nature can induce electron delocalization over the whole
supermolecular architecture, tunable band engineering, as well
as special photophysical properties compared to their pristine
components, offering the opportunity to explore some novel
functions that are suitable for specific applications.[122] Thus,
methods of quantifying the existence of charge transfer are
imperative, and then, we will mainly focus on how to confirm
the CT nature in organic cocrystals, and then introduce some
examples for elucidating the CT–property relationships.
The DCT represents the amount of free electrons from
the donor to the acceptor, which is crucial for physical prop-
erties of their resultant organic cocrystals, but difficulties in
accurately predicting or controlling the DCT are apparent.[14]
The extensively utilized approaches for determination of
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Figure 5.  a) Illustrated structure of TCNQ and fluorinated TCNQ. b) The ground- and excited-state ESR spectra of Spe–TCNB cocrystals. b) Reproduced
with permission.[55] Copyright 2017, Wiley-VCH. c) XPS profiles of Npe, TCNB, and cocrystals. Reproduced with permission.[126] Copyright 2016, Wiley-VCH.
d) Measured current–voltage (I–V) curve and corresponding fitting line for Bpe-IFB. e) Measured I–V curve for Bpe-F4DIB. d,e) Reproduced with
permission.[76] Copyright 2015, American Chemical Society. f) HOMO–LUMO engineering. Schematic positions of donor, CT cocrystal, and acceptor band
structures. g) The absorption spectra of pyrene–TCNB crystals, and their respective constituent materials. g) Reproduced with permission.[60] Copyright
2017, Wiley-VCH. h) PL spectra of Bpe, TCNB, and Bpe–TCNB crystals. Reproduced with permission.[14] Copyright 2015, Wiley-VCH. i) Relationship
between the emission energies of the inclusion crystals (C1–C7) and the ionization potentials of the guest molecules. The linear correlation implies that
the CT complexation dominates the emission. Reproduced with permission.[134] Copyright 2015, American Chemical Society.

the DCT is noticing the bond length variation or stretching
frequencies of some functional groups with the aid of experi-
mental tools, i.e., single X-ray diffraction, and infrared (IR)
and Raman spectroscopy, etc. Impressively, the empirical equa-
tions[115,123] to estimate the DCT have been established due to
the discoveries of various CT materials, as well as the apparent
intramolecular geometry transformation after cocrystallization,
which is helpful for judging the CT nature of a material. For
instance, the DCT in TCNQ and fluorinated TCNQ molecules
(Figure  5a) can be calculated according to the single X-ray
diffraction method,[115] which is shown as follows
DCT = (α CT − α 0 ) / (α −1 − α 0 )(1)
With αi = l3/(l2 + l4), where l is the bond length obtained from
the single-crystal structural analyses and the subscript i = 0, −1,
and CT refers to the neutral molecule, the anion, and the CT
compound, respectively. This method exploits the lengthening
of the formal double bond 3 and the shortening of the formal
single bonds 2 and 4, as the whole structure becomes more
benzenoid in the course of charge transfer, which is suitable
for the transfer range between 0.2e and 0.7e.[115,124] Spectro-
scopic studies, i.e., IR or Raman, are simple and reliable to
detect the DCT from wavenumber changes of certain vibration
modes (e.g., CN stretching frequency), but the DCT should
exceed 0.03 in those cases.[125] Great progress has been made
to estimate the DCT in cocrystals, and some excellent reviews
have addressed the calculation of DCT based on various
methods; therefore, readers are referred to them for additional
details.[9,46,94] However, the limitation of those methods is that
they are merely applied to the TCNQ, TCNQ-like acceptors.
Therefore, particular attention should be paid to the situation

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of how to confirm the CT interaction in other types of cocrys-
tals beyond that. For instance, although the cyano group exists
in TCNB, the wavenumber changes of CN are not obvious
in Raman and FTIR measurements. This may be because the
LUMO of TCNB (−3.92 eV) is higher than the LUMO of TCNQ
(−4.82 eV), making the CT effect in TCNB-type cocrystals weak
relative to the TCNQ-like ones.[126]
To solve this problem, Hu’s group made a comprehen-
sive analysis to reveal the CT interactions in TCNB-type
cocrystals.[14] They conducted more sensitive techniques to
verify the CT interactions. For instance, a relatively weak but
sharp resonance signal is centered at 3473 T in the electron
spin resonance spectrum (ESR) spectrum of Spe–TCNB cocrys-
tals (Figure 5b). According to ESR theory,[127] the g factor is
given by Equation (2)
hγ = gµBHcenter(2)
where h, γ, µB, and Hcenter are the Planck constant, the fre-
quency of the applied microwave magnetic field, the Bohr mag-
netron, and the resonance magnetic field, respectively. Thus,
the g factor is calculated to be 2.005, and is almost equivalent to
the free-electron value of 2.0023, which illustrates the existence
of unpaired electrons and the CT interactions in the Spe–TCNB
cocrystals.[55] This method is also applicable to other cocrys-
tals to detect CT, such as DPTTA–DTTCNQ,[127] Bpe–IFB,[76]
and corannulene-C60,[61] etc. In addition, the X-ray photoelec-
tron spectroscopy (XPS) profile of the cocrystals shows a new
and shifted N1s peak (400.52 eV), as compared with those of
the single component powder (Figure 5c), and clearly dem-
onstrated the appearance of Npe N+ as a result of π-charge
transfer from Npe to TCNB, thus indicating the CT interac-
tions in Npe–TCNB cocrystals.[126] It is should be noted that
XPS method is not yet so widespread,[93] partially because some
solid powder samples are not suitable for operation under
vacuum conditions.
CT interactions are related to some optoelectronic and novel
properties, thus the controllable appearance of CT in organic
cocrystal is very essential. In fact, the CT interaction can be
selectively triggered or suppressed by crystal engineering in
two types of cocrystals grown from similar coformers, which
exhibit distinct optoelectronic characteristics.[76] For instance,
Bpe–IFB wires display distinct photophysical behaviors com-
pared to their single components, which exhibits efficient violet-
blue PL (ΦPL  = 26.1%) with a typical radiation rate constant
kf  = 0.16 ns−1 from the lowest CT1 state (CT1 excitons). More-
over, the 1D Bpe–IFB cocrystals are determined to be semicon-
ducting with an electrical conductivity of 1.42 × 10−6  Ω−1 m−1
(Figure 5d), which is attributed to the π–electron-rich circum-
stances in Bpe columns of Bpe–IFB cocrystals that promote the
CT process from the donor Bpe to the acceptor IFB. Instead,
the CT interactions are suppressed in Bpe–F4DIB cocrystals,
and the photophysical behaviors are related to the Bpe donor,
although the molecular structures of Bpe–F4DIB cocrystals
have changed after cocrystallization. The Bpe–F4DIB cocrystals
are confirmed to be insulators as a result of the CT-free nature
(Figure 5e). Moreover, some novel properties can be observed in
CT cocrystals by the combination of function-free compounds.
For example, the CT effect in the face-to-face mixed-stacking
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system is critical to the generation of organic ferroelectrics, and
the materials can be converted from the paraelectric phase to
the ferroelectric phase by the displacive mechanism under a
coercive electric field.[68,128] Meanwhile, the CT nature of excited
states can induce spatial separation in orbitals and a small sin-
glet–triplet energy gap, which enhances the singlet–triplet spin
mixing and is responsible for efficient reversed intersystem
crossing (RISC). In this respect, Sun et al. have observed ther-
mally activated delayed fluorescence (TADF) in a 1:2 charge-
transfer cocrystal of trans-1,2-diphenylethylene (TSB) and
1,2,4,5-tetracyanobenzene, which opens up a new way for future
design and development of novel TADF materials.[129] It should
be noted that the DCT will affect the properties of the resulting
cocrystal to a large extent; thus, how to regulate the DCT for
achieving a desired property is important. Various studies have
displayed that molecular orbitals (MOs) of the cocrystal are dif-
ferent from, but related to, their parent components. That is,
the highest occupied molecular orbital (HOMO) of the cocrystal
is mostly related to the donor HOMO, whereas the lowest unoc-
cupied molecular orbital (LUMO) of the cocrystal is mainly rel-
evant to the acceptor LUMO.[130,131] In particular, the bandgap of
CT cocrystals is generally narrowed (Figure 5f). Consequently,
the absorption and emission spectra display largely redshifted
and broad profile compared with those of single components
(Figure 5g,h). Thus, the DCT of the cocrystal can be tailed
by changing the HOMO of the donor or the LUMO of the
acceptor, enabling them to have tunable electronic properties
from insulators to superconductors by appropriate molecular
design. It is generally accepted that when the DCT is large,
ranging from 0.5 to 0.74, or there are partially delocalized elec-
trons from the donor to the acceptor, the resulting materials
may exhibit ionic characteristics.[46] Examples like TTF–TCNQ
(650 Ω−1 cm−1)[19,111] and their derivatives possess extraordinary
conductivity and serve as effective organic metal electrodes.[132]
However, when the DCT is small, less than 0.5 or nearly 1,
the cocrystals maybe semiconductors or insulators with infe-
rior conductivity. Jiang and coworkers demonstrated that two
new cocrystals of anthracene–F4TCNQ and tetracene–F4TCNQ
have the same mixed-stacking structure and 1:1 donor:acceptor
stoichiometry but incremental DCT with increasing the donor
HOMO.[133] Therefore, the transport properties of anthracene–
F4TCNQ with the DCT value around ≈0.051–0.089 e cannot
be measured and are determined to be an insulator, while tet-
racene–F4TCNQ with the DCT value around ≈0.086–0.148 e
exhibits p-type semiconducting properties. Moreover, the CT
excitons of the excited states in cocrystals ensure their distinct
optoelectronic properties, which can be tailed by choosing dif-
ferent guest molecules with diverse ionization potential (IP)
values in cocrystallization process. Ono et al. have demonstrated
the linear relationship between the emission energy of the
multi­component crystal and IP of the guest molecule in ternary-
component systems consisting of a naphthalenediimide deriva-
tive (NDI), tris-(pentafluorophenyl)borane (TPFB), and aromatic
molecules (guest) with an NDI:TPFB:guest ratio of 1:2:2. The
emission color is tunable depending on the donor ability (ioni-
zation potential) of the guest molecule (Figure 5i), which can be
attributed to the excited-state CT interactions between the NDI
and the guest molecules in the crystalline state.[134] Alternatively,
the DCT can also be increased by selecting an acceptor with a
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lower LUMO value when fixing the donor and thus different
optoelectronic properties.[24,133]
In summary, research into the CT interactions and their
CT–property relationships is still in its infancy, and tremen-
dous challenges remain at present. For example, 1) the current
methods employed are limited to TCNQ-like cocrystals, and
methods to quantify the DCT value for a wider array of cocrys-
tals are urgently needed; 2) numerous efforts have been made
in building the relationship between CT and conductivity in the
past few decades, and some conclusions have been reached and
mentioned in the above section. However, there is still much
room for development on the relationship between CT and
other functional properties, providing a direction and opportu-
nity for exploring CT cocrystals in the future.
4. Advanced and Emerging Functionality
of Organic Cocrystals
4.1. Optical Functionalities
Organic luminescent materials are endowed with features of
simple-processing capability, low cost, designable ability of
molecular structures, and they have shown booming devel-
opment in the past few decades due to their potential appli-
cations in the fields of OLEDs, OPV, lasers, chemosensors,
etc.[107,135,136] Thus, tuning and controlling the luminescence
behavior of organic solid-state materials for high luminescence
efficiency is extremely urgent. Organic cocrystals are assem-
bled by noncovalent bonds, which are relatively easy to regulate
relative to covalent bonds. Moreover, they are formed by two
or more components, and the introduction of additional mole-
cules may dilute functional groups to avoid aggregation in a
high concentration, which may contribute to increase the lumi-
nous efficiency of the cocrystal compared with the constituent
units. In this section, we will highlight the following optical
functionalities: tunable emission, optical waveguide, and non-
linear optics of organic cocrystals, which will carry new hopes
in future photonics applications.
The tunable emission functionality of organic cocrystals
plays important roles in the fields of multicolor displays, optical
switches, imaging, and solid sources to meet the needs of next-
generation light-emitting materials. The electron cloud rear-
ranges over the whole supermolecular architecture and new
MOs of cocrystals will be obtained when a cocrystal is formed;
thus, the luminescence behavior will be altered correspondingly.
The modulation of the luminescence behavior in an organic
cocrystal includes the regulation of color, lifetime, photo­
luminescence quantum yield (PLQY), the radiation constant
(kf), etc. As for the luminescent color, the wavelength of the
cocrystals may be redshifted or blueshifted relative to a single
component. The targeted color can be achieved by a judicious
choice of donor and acceptor components. For example, when
using the same donor mole­cule and selecting different acceptor
molecules, the cocrystal luminescent color will vary. Yan and
coworkers have reported systematic color tuning of p-BCB with
six diverse acceptor coformers by a cocrystallization method.
The color from blue, to green, to yellow can be finely modified
by appropriate design of the interaction type (e.g., hydrogen and
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halogen bonds), providing a facile way to design and develop
new types of solid multicolor fluorescent organic materials.[108]
Generally, the emission spectrum of the resulting CT cocrystal
exhibits a redshifted trend to the region of long wavelength due
to a narrowed band relative to those of their components, thus
different noncovalent interactions between the D and the A can
effectively tune and control the luminescent behaviors of the
cocrystals. Moreover, it is also feasible to use a “doping” strategy,
commonly used in OLEDs, to tune the luminescence efficiency
and emission colors of cocrystals. The dopant can interact with
one of the components of the cocrystal to form a mixed complex,
and the desired emission color can be tailored by adjusting the
dopant concentration in an efficient Förster resonance energy
transfer (FRET) process. For instance, Liao and coworkers have
obtained the regulation of color from blue through pure white
to orange (Figure  6a) in (pyrene)x(naphthalene)1−x(TCNB) by
using pyrene as dopant.[137] Encouragingly, Hu and coworkers
have explored the rational design of multicolor cocrystals on the
basis of the competition of arene–perfluoroarene and CT inter-
actions. In detail, the emission spectrum of pyrene–octafluoro-
naphthalene (pyrene–OFN) assembled by AP interactions has
a good overlap with the absorption spectrum of pyrene–TCNB
formed by CT interactions; therefore, the emission energy of
pyrene–OFN can be reabsorbed by pyrene–TCNB after TCNB
molecules doping into pyrene–OFN. The emission colors of
the mixed CT complex can be tailored due to efficient energy
transfer between the energy donor (pyrene–OFN) and acceptor
(pyrene–TCNB) by their competitive intermolecular interac-
tions (Figure 6b).[60]
In addition to focusing on the color variance in the donor–
acceptor cocrystallization process, other emission character-
istics, i.e., lifetime, PLQY, and the radiation constant (kf), are
also important for the selection of functional materials. Wu
et al. demonstrated that the fluorescence lifetime (0.9 ns) of
p-BCB:F4DIB micro-cocrystals is much lower than that of
pure p-BCB microcrystals (14.0 ns), but their obtained kr
of the p-BCB:DIFB micro-cocrystals (0.12 ns−1) is much larger
than that of the p-BCB microcrystals (0.04) ns−1 by a cocrystal
approach. The resulting distinct photophysical properties can
be attributed to the absence of excimers in the cocrystals.[138]
Moreover, the cocrystallization strategy can also regulate the
emission behavior of the spin-forbidden triplet state. Typi-
cally, Kim and coworkers have reported a “direct heavy atom
effect” principle for the design and synthesis of purely organic
phosphorescent materials by crystal design, wherein the prod-
ucts are color-tuned to emit blue, green, yellow, and orange
(Figure 6c). Impressively, they introduce a host of Br6 with a
similar size to dilute the phosphorescence emitter of Br6A
molecules to avoid their self-quenching, achieving a high value
(55%) of room-temperature phosphorescent quantum yield.[30]
Optical waveguides utilize the refractive indexes of the
media in the waveguide region to be higher than that of their
environment. Therefore, they can effectively confine, propa-
gate, and couple light in the waveguide region.[139–141] Organic
materials can serve as active optical-waveguide resonators
and offer the opportunity to improve the waveguiding diver-
sities compared with passive optical-waveguide materials,
playing important roles in integrating optical logic circuits
as fundamental elements and interconnects.[142–144] Organic
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 6.  a) Emission colors in a CIE 1931 chromaticity diagram: 0 (blue), 0.015% (white), and 0.1% (orange). Reproduced with permission.[137] Copyright
2012, Wiley-VCH. b) Representation of the energy-transfer mechanism and the tunable fluorescence microscopy images of pyrene–OFN microwires.
Reproduced with permission.[60] Copyright 2017, Wiley-VCH. c) Photographs of BrC6A/BrC6, Br6A/Br6, Np6A/Np6, and BrS6A/BrS6 (clockwise from
top left) mixed crystals, each containing ≈1 wt% aldehyde chromophore and 99 wt% analogous host compound. Crystals are shown under 365 nm UV
light. Reproduced with permission.[30] Copyright 2011, Nature Publishing Group. d) PL microscopy image of Bpe–TCNB under excitation. Reproduced
with permission.[14] Copyright 2015, Wiley-VCH. e) Optical image of the individual 2D organic microcrystal and the fluorescence microscopy image
of the individual 2D organic cocrystal by exciting the geometric center with a focused laser (λ = 375 nm). Reproduced with permission.[145] Copyright
2018, Wiley-VCH. f) The corresponding PL images when the excitation laser is moved (λ  = 374 nm). Reproduced with permission.[126] Copyright
2016, Wiley-VCH. g) The upconversion PL spectra of Spe crystal. Reproduced with permission.[120] Copyright 2016, Wiley-VCH. h) The upconversion
PL spectra of STC cocrystals and i) the corresponding linear relationship between the PL intensity and excitation power (W2). h,i) Reproduced with
permission.[55] Copyright 2017, Wiley-VCH.

cocrystals are favorable for the formation of regular mor-
phology due to the good regulation of noncovalent bonds,
which are beneficial to investigate the physical properties
along isotropic/anisotropic molecular packing directions. For
example, Zhu et al. have demonstrated that the 2D morphology
of the Bpe–TCNB cocrystal exhibits an isotropic optical-wave-
guide property (Figure 6d). The optical propagation loss coef-
ficients (R) in two directions are almost the same, which is
not related to the molecular packing structure.[14] However,
Zhuo et al. have explored the asymmetric photon-transport
characteristic in a 2D halogen-bonded cocrystal based on DPEpe
and F4DIB due to the anisotropic organic molecular packing.
That is, 2D DPEpe–F4DIB cocrystals demonstrate a symmetric
optical waveguide with the same optical-loss coefficients of
RUpward  = 0.0344 dB µm−1 and RDownward  = 0.0333 dB µm−1
along the[100] crystal direction, as well as a novel asymmetric
optical waveguide with different optical-loss coefficients,
RBackward  = 0.0346 dB µm−1 and RForward  = 0.0894 dB µm−1
along the [010] crystal direction (Figure 6e).[145] Therefore, we
can draw a conclusion that organic cocrystals indeed provide a
platform to investigate the direction-oriented optical transport
properties, which can contribute to constructing a microscale
optical logic gate with multiple input/out channels. As demon-
strated by the following example, Zhu et al. adopted a “probe-
assisted crystal moving” technique to randomly build desired
“cocrystal waveguide couplings” (CWCs), and the output color
(yellow, blue, and white) of the C position can be tailored by
choosing diverse input positions (Figure 6f).[126] That is, when
the NTC is excited by the laser, yellow PL originating from the
NTC can be coupled from the NTC into the BIC and propa-
gate in both cocrystals, and the output color of the C position
is yellow. When the BIC is excited, blue PL originating from
the BIC can propagate along with the 1D BIC, and the output
color of the C position is blue. When both the input A and

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www.advancedsciencenews.com
B positions are excited, a white-light emission at output C is
observed due to a energy-transfer process from the BIC to the
NTC.
Nonlinear optical functional materials can be yielded by
manipulating the cocrystallization strategy, which provides an
effective way to design and develop novel materials on non-
linear optical applications for future optoelectronics. Second-
harmonic generation (SHG) is a common and important
energy-conserved process, which can transfer of the incident
fundamental frequency (ω) of the light into radiation having
twice the frequency (2ω).[146] It is well known that an asym-
metric structure is an essential prerequisite for realizing SHG
properties; thus, the symmetry of the resulting materials after
cocrystallization is of paramount importance. SHG properties
can be suppressed or generated by introducing additional com-
ponents in cocrystal engineering. Recently, Zhu et al. demon-
strated that SPE molecules exhibit SHG properties owing to the
D–A configuration of the SPE molecule with intramolecular
electronic polarization being centrally asymmetric (Figure 6g),
while SHG properties are absent in the Spe–F4DIB cocrystal
with a centrosymmetric P21/n crystal space group.[120] Yan
et al. have reported that the pristine 2,5-diphenyloxazole (DPO)
shows no SHG behavior, but the formation of four cocrystals
can transform into SHG-function materials due to the non-
centrosymmetric structure of the crystal.[147] In addition, the
two-photon absorption property is an example of the third-
order nonlinear optical effect, which has intriguing application
prospects in the field of 3D fluorescence imaging, optical data
storage, optical limiting, and lithographic microfabrication,
etc.[148–150] Organic cocrystals are synthesized by noncovalent
bonds, and the TPA-function materials can be prepared by elab-
oratively selecting constituent monomers and manipulating
noncovalent bonds. Similar to the traditional synthesis method,
cocrystallization also allows some functional core skeletons to
be used as the constituent donors in organic cocrystals, which
can assemble with some small-molecule acceptors. Then,
the properties of the cocrystals can inherit the properties of
the original components.[108] Stilbene and its derivatives,
as the typical representative of TPA molecules, have been exten-
sively studied in the liquid state.[151] However, the TPA perfor-
mance of solid-state stilbene-type materials is rarely explored.
Impressively, Sun et al. have put forward a cocrystal strategy to
yield TPA properties in stilbene-type cocrystals (Figure 6h,i).[55]
The Spe–TCNB cocrystals exhibit the unique TPA property
than that of the constituent units, and it is demonstrated that
the two-photon absorption properties originate from intermo-
lecular charge-transfer (ICT) interactions in the D–A system.
4.2. Electrical Functionalities
As an indispensable part of modern technology, the develop-
ment of electronics has been an encouraging research topic
for decades, and they are included in diverse fundamental elec-
tronic devices, such as field-effect transistors, light-emitting
diodes, solar cells, memory devices, sensors, and so on.[8,152,153]
Such a diversity of electronic applications calls for a higher
standard of functional materials. Over decades of develop-
ment, organic cocrystals are found to be attractive candidates
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for functional electronic materials, with great advantages of low
cost, low temperature, and facile processing, as well as fasci-
nating electronic properties, and they display great potential
in electronic applications including in organic field-effect tran-
sistors, organic photodetectors, organic photovoltaics, organic
light-emitting transistors, and so on.[18]
The OFET, a fundamental element of electronic circuits,
holds promise for innovative applications, such as for amplifiers,
electronic papers, active-matrix displays, and radio-frequency
identification (RFID) cards.[154] To date, plenty of efforts have
been devoted to the materials science, and tremendous achieve-
ments have been gained in semiconductor material design
with high-performance hole-transport, electron-transport,
and ambipolar charge-transport properties.[155] In comparison
with others, ambipolar materials are more attractive, as they
integrate hole- and electron-transport properties together,
which are promising in the construction of logic circuits.[81]
However, their development has fallen behind the others due to
the indefinite design strategies and complicated synthesis pro-
cedures. In contrast, cocrystal engineering offers an alternative
approach toward ambipolar materials, which turns out to
be the simplest and most effective strategy. Typically, when
p-type molecules (donors) and n-type molecules (acceptors)
recognize each other and coassemble together, a cocrystal
with molecular-level heterojunction structure would come out,
which could be in favor of hole and electron transportation
simultaneously. Moreover, the formation of cocrystals also leads
to an effective modulation of the bandgap, which is beneficial to
energy matching between the cocrystal frontier orbitals, as well
as the work function of the injected electrodes, and hence is in
favor of efficient charge injection.[156] Typical ambipolar exam-
ples are represented for the BEDTTTF–TCNQ cocrystal,[157] the
CoTMPP–C60 cocrystal,[158] and the DPP2P–NDI81 cocrystal.[92]
In comparison with single-component semiconductors,
cocrystals display a different donor–acceptor structure, and
hence a unique charge-transport mechanism. In segregated-
stacking cocrystal systems, each donor or acceptor column
serves as an efficient charge-transport pathway for holes or
electrons, respectively, deriving from their direct π-electron
coupling. A typical example is the cocrystal composed of meso-
diphenyltetrathia[22]-annulene[2,1,2,1] (DPTTA) and C60,[76]
wherein an alternating layer-by-layer packing of DPTTAs and
C60s forms. As a consequence, the cocrystal exhibits significant
ambipolar charge transport with high mobility of 0.3 cm2 V−1 s−1
for the hole (Figure  7a) and 0.01 cm2 V−1 s−1 for the electron
(Figure 7b).
While in mixed-stacking systems, the donor and the acceptor
stack alternatively in a face-to-face motif. Such kinds of cocrys-
tals may also display outstanding ambipolar charge-transport
properties even without continuous donor or acceptor mole­
cular π-stacking, and that contributes to the super-exchange
mechanism.[159,160] That is, the frontier orbitals of an acceptor
can mix with the orbitals of its adjacent acceptor through the
bridging of their inside donor molecule, and hence provide
efficient electron-transport channels. Similarly, the mixing
frontier orbitals of the two closest donors and the bridging
acceptor would offer effective hole-transport channels. Conse-
quently, mixed-stacking cocrystal systems are also available for
excellent ambipolar charge-transport materials. One classical
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 7.  The electronic functionalities of cocrystal. a) The hole-transport channels and b) electron-transport channels in segregated-stacking DPTTA-C60
cocrystal. c) The hole-transport channels and d) electron-transport channels in mixed-stacking DPTTA-TCNQ cocrystals. e) The photoresponse behaviors
of organic cocrystal. e) Reproduced with permission.[102] Copyright 2015, Wiley-VCH. f) The photovoltaic effects of organic cocrystals. Reproduced
with permission.[171] Copyright 2016, Wiley-VCH. g) An organic light-emitting transistor based on high-mobility emissive cocrystal. Reproduced with
permission.[176] Copyright 2017, Wiley-VCH. DPTTA-C60, Refcode 954665 from CSD. Note: The Refcode number refers to the crystal number in the
Cambridge Crystallographic Data Centre (CCDC).

case is the mixed-stacking DPTTA–TCNQ cocrystal,[104] which
exhibits high-performance ambipolar charge transport with
hole mobility of 0.04 cm2 V−1 s−1 and electron mobility of
0.03 cm2 V−1 s−1. Theoretical calculations demonstrate that
along the donor–acceptor π-stacking direction, there is no direct
electronic coupling. In sharp contrast, with consideration of the
super-exchange effect, the calculation results display effective
electronic couplings with large transfer integrals (Figure 7c,d).
Zhu’s group developed an extended π-conjugated TCNQ deriv-
ative acceptor, 4,8-bis(dicyanomethylene)-4,8-dihydrobenzo[1,2-
b:4,5-b′]-dithiophene (DTTCNQ), which can also cocrystallize
with DPTTA molecules with a 1:1 stoichiometry ratio.[104] Similar
to the DPTTA–TCNQ cocrystal, DPTTA and DTTCNQ mol-
ecules stack alternatively and induce a super-exchange effect.
Moreover, the DTTCNQ’s extended π-conjugated structure also
leads to a direct lateral π–π coupling among intercolumnar
DPTTAs or DTTCNQs. Both the super-exchange effect and the
direct coupling contribute to the construction of a quasi-2D
charge-transport network. Consequently, a remarkable
improvement of ambipolar charge-transport characteristics is
observed in DPTTA–DTTCNQ cocrystals with hole mobility
of 0.77 cm2 V−1 s−1 and electron mobility of 0.24 cm2 V−1 s−1.
In another case, shown in DPTTA–TCNQ, F2TCNQ, and
F4TCNQ cocrystal systems,[24] with the increase of the electron-
accepting ability of the acceptors, that is, with the enhancement
of CT features, the calculated transfer integrals rise, indicating
the improvement of the super-exchange coupling effect. Mean-
while, in accordance with theoretical calculations, their charge-
transport mobilities display a clear tendency that they indeed
grow with the improvement of CT degree.
Organic photodetectors, which transfer photo signals into
electrical signals, are in broad-prospect applications such as
optical imaging, environmental monitoring, optical communica-
tions, and remote control, etc.[161–163] A photodetector device nor-
mally undergoes several processes and an ideal photo­active layer
should ensure efficient photon absorption, exciton dissociation,

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www.advancedsciencenews.com
and charge-carrier transport simultaneously.[164,165] Organic
cocrystals are excellent candidates for photodetectors for the fol-
lowing points: 1) their absorptions are dependent on the newly
formed energy states. Especially, the generated CT state in CT
cocrystals would contribute to the redshift absorption, and hence
unusual IR absorption.[166] The tailorable absorption provides a
shortcut toward the design of optical functional materials and
the fabrication of wavelength-selective photo­­­­­detector devices.
2) In a cocrystal structure, there are plenty of molecular-scale
donor–acceptor interfaces, which is beneficial for efficient
exciton dissociation. 3) The π–π overlapping in donor–acceptor
cocrystals provides effective transport pathways for both holes
and electrons, and that significantly facilitates charge-carrier
transport and collection simultaneously. 4) With regular donor–
acceptor stacking structures, cocrystals provide a promising tool
to study the intrinsic photoresponse characteristics of organic
D–A systems. For instance, Pei’s group[167] has developed a
photo­conductor device based on a mixed-stacking cocrystal cou-
pled with the photoinduced electron-transfer phenomenon. In
the cocrystal system, the significant D–A interaction results in
the localization of charges under the dark state and restrains
the charge-carrier movement. However, the specific D–A mole-
cular structure leads to its strong ionization, and that prevents
the unbeneficial recombination process, wherein the further
dissociated carrier transport contributes to the photoconductive
property. Zhu found that P1T1 demonstrates a higher photore-
sponsivity than P3T1,[102] although they are composed of the
same molecules, demonstrating that the photoresponse property
is closely related to the molecular arrangement. In detail, two
cocrystals have similar absorption spectra, as well as comparable
charge-carrier transport ability, which stand for the equal photon
absorption and carrier-transport efficiency. Therefore, the photo­
response property difference is attributed to the exciton dissocia-
tion process, indicating that the P3T1 packing structure maybe
unfavorable for efficient exciton dissociation (Figure 7e).
Organic photovoltaics, a promising application in next-gener-
ation energy-harvesting technology, have attracted considerable
attention with great advantages of tailored molecular structures,
low cost, solution processability, light weight, flexibility, large-
area fabrication techniques, and so on.[144,168–170] However, the
short exciton-diffusion length, the small donor–acceptor inter-
face, and the discontinuous carrier-transport pathways restrain
the photovoltaic effect of organic materials. Fortunately, organic
cocrystals serve as an ideal photovoltaic active layer, which ena-
bles: 1) strong photon absorption; 2) enough donor–acceptor
interfaces, hence lowering the requirement for the exciton-
diffusion length; 3) efficient charge-carrier transport; and 4) a
smooth surface for good interface contact. Nuckolls and
coworkers[38] explored the formation of donor–acceptor cocrys-
talline regions in organic heterojunction solar cells, which would
drastically improve the device power conversion efficiency.
They chose hexabenzocoronene (12-c-HBC) as a donor and
phenyl-C70-butyric acid methyl ester (PC70BM) as an acceptor.
With complementary shapes, the donor and acceptor are prone
to self-assembly and form a molecular-scale p–n junction,
which greatly increases the power conversion efficiency. More-
over, the donor–acceptor stoichiometry is also responsible for
the film morphology and hence the performance of the solar
cells. Zhang et al.[171] reported the first photovoltaic device
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based on an organic cocrystal (Figure 7f). They selected the
segregated DPTTA–C60 cocrystal as the active layer, with two
main considerations: one is that the DPTTA layer and the C60
layer stack alternatively, resulting in uniform molecular-scale
heterojunction layers. This would promote the exciton diffusion
and dissociation process. The other is the excellent ambipolar
charge-transport capability of DPTTA–C60, which is essential
in photovoltaic devices. As expected, the power conversion
efficiency of the cocrystal is more than 140 times higher than
the corresponding bilayer heterojunction photovoltaic cell,
indicating the great potential applications of cocrystals in the
advanced organic photovoltaic field.
The organic light-emitting transistor is an emerging opto-
electronic device that integrates the light-emitting functionality
of an OLED and the electrical switching capability of an OFET
in a single device.[172–174] Therefore, a high device-integration
degree would significantly reduce the fabrication processes and
technological requirements in practical applications, and is then
in favor of low-cost, large-area, high-throughput production.
However, the advanced OLET device sets up a high standard
for the active functional material, which should ensure efficient
light-emitting and charge-transport functionality simultaneously.
As discussed above, organic cocrystals display great potential in
diverse optoelectronic applications. Meanwhile, they are prom-
ising in integrating different optoelectronic functionalities and
demonstrating multifunctional properties.[175] Consequently,
cocrystal engineering serves as an alternative strategy toward
high-mobility emission materials, which are good candidates for
advanced OLET applications. Park’s group[103] has successfully
designed a highly luminescent and ambipolar-charge-transport
cocrystal. They chose two isometric molecules 4M-DSB and CN-
TFPA as donor and acceptor, respectively, with considerations of:
1) high luminescence; 2) sufficient solubility; 3) dense packing
without bulky substituents; 4) similar chemical structures;
5) potential π–π interactions and hydrogen bond interactions; and
6) maximum molecular orbital offset. Consequently, the donor
and acceptor molecules are prone to self-assembly and form a 1D
mixed-stacking CT cocrystal by solvent vapor annealing (SVA).
The cocrystal not only displays efficient red luminescence with
a PLQY of 31%, but also demonstrates high-performance ambi-
polar charge-transport properties, and thus holds promise for
next-generation optoelectronic applications. Subsequently, they
followed this strategy and designed a new 2:1 mixed-stacking CT
cocrystal with uniform 2D morphology (Figure 7g).[176] With dense
packing and rigidified structure in the 2D stacking, the cocrystal
displays a low nonradiative rate and a high PLQY of 60%. More-
over, its 2D morphology also facilitates the conformal contacts in
corresponding OFET devices, which demonstrates well-balanced
ambipolar charge transport. These together make the cocrystal
available for fascinating electroluminescence applications. There-
fore, they fabricated the first OLET device based on CT cocrystals
with an external quantum efficiency as high as 1.5%, which is the
highest among single-layer active-channel OLETs, indicating a
promising potential in future lighting applications.
4.3. Innovative Functionalities
Apart from developing efficient design principles for high-
performance functional materials in current optoelectronic
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applications, taking advantage of this useful strategy in a
broadened research field is also required to enrich their inno-
vative applications. Taking the organic photothermal (PT) field
as an example, PT materials, which are available to convert
infrared light energy into heat energy, have great potential in
various applications involved in photothermal therapy, photo–
thermal–electric devices, photothermal/photoacoustic imaging
and shape-memory devices.[177–180] However, for a long period
of time, the development of the organic PT field has been
restricted by the limited kinds of PT materials. Therefore, there
is an urgent demand to develop new strategies and solve this
problem.[39] In this respect, Wang et al. developed a cocrystal
strategy to fabricate a new PT material with a facile prepara-
tion method (Figure  8a). The CT interactions of the DBTTF–
TCNB cocrystal (DTC) in both the ground state and the excited
state make it a narrow-bandgap material, corresponding to its
significant redshifted near-infrared (NIR) absorption. At the
same time, the excited states of DTC prefer to undergo rapid
nonradiative decay, while the radiative transition processes
are inhibited with efficient fluorescence quenching in the
solid state. Attributed to these characters, DTC demonstrates
high-performance PT conversion properties with high cycling
stability. Meanwhile, it also shows great potential in encouraging
nondestructive PT imaging with real-time and time-resolved
response (Figure 8b). In addition, novel stimuli response prop-
erties are also explored in organic cocrystals. Typically, Sun
et al. have demonstrated that macroscopic mechanical bending
of the binary perylene–TCNB cocrystal is achieved when
exposed to a high concentration of THF solvent/vapor. They
clearly explained that the solvatomechanical bending behavior
is driven by structural change at the molecular scale, for the
first time, providing a desired platform to investigate the mech-
anism of mechanical motion of cocrystals induced by guest
molecules (Figure 8c).[181] Consequently, with a facile design
solution, as well as a simple preparation process, the develop-
ment of cocrystal engineering critically paves the way to design
some innovative functional materials, which promotes the
enlargement of functional cocrystals.
5. Conclusions and Outlook
Recently, cocrystal engineering, as an emerging functional
material-design strategy, not only has the advantages of non­
covalent bond synthesis with low cost, structural flexibility, and
solution-processing capability, but also provides opportunities

Figure 8.  a) Photothermal conversion curves of cocrystals under 808 nm laser irradiation (0.7 W cm−2). b) IR camera images of cocrystal-patterned
letters TJU. a,b) Reproduced with permission.[39] Copyright 2018, Wiley-VCH. c) Reversible structural and color changes between ternary PT2TC and
binary PTC and the schematic diagram of mechanical bending of a cocrystal rod (“+” represents the inclusion of THF, “−” displays the removal of
THF). Reproduced with permission.[181] Copyright 2017, American Chemical Society.

Adv. Mater. 2019, 1902328 1902328  (18 of 22) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
to explore novel photophysical phenomena. This greatly sim-
plifies the design ideas and preparation methods of functional
materials, and thus improves the preparation efficiency of
materials, attracting much attention in the field of materials
and devices. Herein, we first focused on the assembly of cocrys-
tals to effectively realize cocrystallization, including the internal
driving forces (e.g., the important noncovalent interactions) and
external factors (e.g., the growth methods), which is conducive
to obtaining high-quality and high-performance cocrystals. It
is hoped to provide a reference for improving assembly effi-
ciency and laying the foundations for studying the properties of
cocrystals. Subsequently, we discussed the influencing factors
(the packing structure and CT nature) of cocrystal properties
to give some general guidance, and promote the development
of functionality-oriented cocrystal design. Finally, some optical,
electrical, and innovative properties in organic cocrystals were
presented, showing the great advantages and application pros-
pects of cocrystals for constructing functional materials. It is
undeniable that the field of organic cocrystals is booming and
promising. However, as a novel research field, some challenges
need to be settled to realize practical applications of organic
cocrystals. 1) Assembly. Future studies need to further explore
the balance of each force and strive for controllable modula-
tion of intermolecular forces, and further reveal the mecha-
nism of cocrystallization for achieving controllable preparation
of cocrystals. At the same time, the growth method should be
broadened to enable cocrystals to achieve large-scale, low-cost,
highly ordered arrays or thin-films for practical applications.
2) Functionality-related factors (e.g., the packing structure and
CT nature). It is urgent to explore more research systems with
diverse properties to provide a comprehensive understanding of
the relationship between structure and properties. Meanwhile,
regulating the criteria for quantitatively determining DCT
values in a large amount cocrystals and some empirical for-
mulae are extremely necessary, thereby increasing the predict-
ability of cocrystal functionalities. 3) Functionalities. Improving
the cocrystal performance in the developed functional fields,
e.g., in terms of OFET devices, the performance of cocrystal
materials is inferior to that of single-component materials, and
thus the crystal quality, device preparation, and charge-transport
paths needs to be continuously optimized and fully developed
in cocrystals. Moreover, it should further broaden the possi-
bility of cocrystal applications in other fields (such as electrically
pumped organic lasers or quantum wells), and thus promote
the development of cocrystals in multifunctional applications.
Acknowledgements
L.S. and Y.W. contributed equally to this work. The authors acknowledge
financial support from the Ministry of Science and Technology of
China (Grants 2016YFB0401100 and 2017YFA0204503), the National
Natural Science Foundation of China (51702297, 51633006, 51725304,
51733004, and 51703159), and the Strategic Priority Research Program
of the Chinese Academy of Sciences (Grant No. XDB12030300).
Conflict of Interest
The authors declare no conflict of interest.
Adv. Mater. 2019, 1902328 1902328  (19 of 22)
www.advmat.de
Keywords
charge transfer, functionality, noncovalent-bond assembly, organic
cocrystals, packing structures
Received: April 11, 2019
Revised: May 27, 2019
Published online:
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