Emergent Self-Assembly Pathways to Multidimensional Hierarchical Assemblies using a Hetero-Seeding Approach

Article abstract of DOI:10.1002/chem.201903066

The controlled formation of complex and functional 1-, 2-, and 3D hierarchical assemblies from molecular building blocks represents a key current challenge. Herein, we report the use of a seeded growth approach for a series of perylenediimide-based molecules (PDIs 1–4) to access otherwise inaccessible self-assembly pathways that yield complex hierarchical structures. The key to the new approach is to use hetero-seeds which possess a different composition and morphology from that of the molecular building block. For example, a nanotube seed (from PDI 3) and a microribbon seed (from PDI 4) were found to initiate different self-assembly pathways for PDI 1, which normally assembles to yield nanocoils. This led to the formation of unprecedented 3D scroll-like and scarf-like hierarchical nanostructures, respectively. Also, the hetero-seeds from PDI 3 initiate hidden self-assembly pathways of PDI 2 to generate 1D tubular heterojunctions. Significantly, this new strategy offers new opportunities to create emergent and functional hierarchical and complex structures from small molecule precursors.

Full text of DOI:10.1002/chem.201903066

A Journal of
Accepted Article
Title: Emergent Self-assembly Pathways to Multidimensional
Hierarchical Assemblies via a Hetero-seeding Approach
Authors: Yin Liu, Yanjun Gong, Yongxian Guo, Wei Xiong, Yifan
Zhang, Jincai Zhao, Yanke Che, and Ian Manners
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To be cited as: Chem. Eur. J. 10.1002/chem.201903066
Link to VoR: http://dx.doi.org/10.1002/chem.201903066
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10.1002/chem.201903066
Chemistry - A European Journal
Emergent Self-assembly Pathways to Multidimensional
Hierarchical Assemblies via a Hetero-seeding Approach
Yin Liu, Yanjun Gong, Yongxian Guo, Wei Xiong, Yifan Zhang,* Jincai Zhao, Yanke Che,* and Ian
Manners
assembled molecular building block, the nucleation barrier
can be bypassed.[14, 15, 25-27, 30-34] In such cases the morphology
of the resulting thermodynamically stable assemblies is
independent of whether growth proceeds in the presence or
absence of seeds. The analogous use of hetero-seeds, which
possess a different composition or morphology to the
assembled molecular building block, is much less explored.
Nevertheless, examples of the formation of hierarchical
assemblies such as scarf and core-segmented fibers and
platelets have been reported for crystallizable polymer or π-
stacking molecular systems using this approach.[2,12,24] The
formation of 1-D and 2-D heterostructures based on small
organic molecules have also been reported.[34,35] Notably, in
general, the morphology of stable assemblies via seeded self-
assembly is the same as those formed via unseeded self-
assembly, i.e., being independent of the added hetero-seeds
even although they grow on hetero-seeds. So far, in one case
the origin of the seed has been shown to dictate the
morphology of the resulting block copolymer (BCP)
nanostructures via a morphological memory effect.[4] Recently,
Sugiyasu and Takeuchi and coworkers reported that
mechanical agitation and a seeding method enabled the
differentiation of a metastable porphyrin supramolecular
assembly in one and two dimensions.[13] These observations
inspired us to envisage that some small molecules may
possess multiple self-assembly pathways, including those
with a high energy barrier that cannot be accessed via
unseeded self-assembly. Exploration and realization of such
hidden self-assembly pathways for small molecules via the
seeding method may lead to a variety of unprecedented
nanostructures. However, two challenges hinder the
implementation of such an approach: (1) access to small
molecules with multiple hidden self-assembly pathways and
(2) the formation of easily accessible seeds that can function
as initiators.
The controlled formation of complex and functional 1-, 2-,
and 3-D hierarchical assemblies from molecular building
blocks represents a key current challenge. Herein, we
report the use of a seeded growth approach for a series of
perylenediimide-based molecules (PDIs 1 - 4) to access
otherwise inaccessible self-assembly pathways that yield
complex hierarchical structures. The key to the new
approach is to use hetero-seeds which possess a different
composition and morphology from that of the molecular
building block. For example, a nanotube seed (from PDI
3) and a microribbon seed (from PDI 4) were found to
initiate different self-assembly pathways for PDI 1, which
normally assembles to yield nanocoils. This led to the
formation of unprecedented 3D scroll-like and scarf-like
hierarchical nanostructures, respectively. Also, the
hetero-seeds from PDI 3 initiate hidden self-assembly
pathways of PDI 2 to generate 1D tubular heterojunctions.
Significantly, this new strategy offers new opportunities to
create emergent and functional hierarchical and complex
structures from small molecule precursors.
Living
crystallization-driven
and
supramolecular
polymerizations performed under conditions of kinetic control
have recently emerged as a promising seeded growth approach
to access 1D and 2D hierarchical structures with controlled
dimensions and segmented architectures. These methods have
been
extensively
demonstrated
for
amphiphilic
homopolymers and block copolymers with crystallizable
core-forming segments[1-12] and also π-stacking and hydrogen-
bonding molecular amphiphiles.[13-35] In the latter case the
systems generally involve the presence of a relatively slow
transformation from
a
kinetically trapped to
a
thermodynamically stable state.[13-35] However, through the
use of homo-seeding methods which involve the addition of a
seed with the same composition and morphology as the
Herein we demonstrate that, in addition to their unseeded
self-assembly pathway, perylenediimide-based molecules
(PDIs 1 and 2) possess hidden self-assembly pathways with a
high energy barrier (Figure 1). Although these emergent self-
assembly pathways cannot be accessed using mechanical
agitation, they become active on the addition of different
hetero-seeds (of PDIs 3 and 4) to yield complex hierarchical
assemblies with unusual morphologies (Figure 1). We also
demonstrate that the existence of the hidden self-assembly
pathways is related to the competitive intermolecular
interactions that are encoded in the molecular structure of
small molecules. This represents an advance in seeded self-
assembly of small molecules which allows opportunities to
access to a range complex and emergent architectures.
Ms. Y. Liu, Mr. Y. J. Gong, Mr. Y. X. Guo, Mr. W. Xiong, Prof. Y.
Che, Prof. J. Zhao.
Key Laboratory of Photochemistry, CAS Research/Education
Centre for Excellence in Molecular Sciences, Institute of
Chemistry, Chinese Academy of Sciences, Beijing, 100190,
University of Chinese Academy of Sciences, Beijing, 100049,
China
E-mail: ykche@iccas.ac.cn
Dr. Y. Zhang, Prof. I. Manners
School of Chemistry, University of Bristol, Bristol BS8 1TS, UK
Department of Chemistry, University of Victoria, Victoria, V8W
3V6, British Columbia, Canada.
E-mail: yifan.zhang@bristol.ac.uk
DOI: 10.1002/adma.2014XXXXX
1
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10.1002/chem.201903066
Chemistry - A European Journal
Figure 1. (a) Schematic illustration of the hidden self-assembly pathways of PDI 1 together with its unseeded self-assembly pathway.
(b) Schematic illustration of the hidden self-assembly pathway of PDI 2 together with its unseeded self-assembly pathway. (c)
Molecular structures of PDIs 1-5.
We previously reported the 1D and 2D self-assembly of
PDI 3 in the absence of seeds, the presence of homo-seeds,
and hetero-seeds consisting of microribbons from PDI 4. In
each case, 3 self-assembled into a similar nanotube
morphology.[34-35] This suggested that PDI 3 likely has no
other accessible self-assembly pathways between kinetically-
trapped microribbons and thermodynamically stable
nanotubes. Given that the competition between molecular
interactions determines the energy landscape that governs the
self-assembly pathways[28,37], we anticipated that the reduction
of the steric hindrance of the substituents in PDI 3 might lead
to more relatively stable states. To verify this, we prepared
PDI 1 bearing an ethoxy group at the 2-position of the phenyl
substituent (Figure 1c). However, even under mechanical
agitation, PDI 1 only exhibited one self-assembly pathway
involving the evolution from kinetically trapped metastable
microribbons to stable nanocoils in the unseeded self-
assembly process (Figures 1a and S1). This observation
indicated that other self-assembly pathways (if they exist)
possess a high energy barrier to nucleation and thereby cannot
be accessed under unseeded self-assembly conditions. To
address this issue, we explored the utilization of hetero-seeds
with different compositions and crystal structures. Two sets of
hetero-seeds were fabricated by ultrasonicating the
three days. The nanotube seeds from PDI 3 possessed a
diameter of ca. 45 nm (Figure S2a) similar to that of the
pristine nanotubes (Figure S2b) and lengths from 0.2 to 1.2
μm. Microribbon seeds from PDI 4 possessed widths ranging
from 1.0 to 2.5 μm and lengths from 5 to 50 μm (Figure S3).
Next, we explored the use of these seeds to induce the self-
assembly of PDI 1.
Living growth of PDI 1 using nanotube seeds derived
from PDI 3. Initially, we explored the seeded self-assembly
of PDI 1 by using nanotube seeds from PDI 3 as initiators.
Specifically, the prefabricated stock solution of metastable
microribbons from PDI 1 (Figure S1a) was first prepared by
adding a chloroform solution of PDI 1 into ethanol (1:15 (v/v)
chloroform/ethanol) and aging for 2 h. Then nanotube seeds
from PDI 3 with average length of ca. 1 μm in 1:15 (v/v)
chloroform/ethanol were added into the above stock solution.
Surprisingly, monomer 1 was observed to nucleate and grow
on the side of the nanotubular seeds to form scroll-like 3D
structures with a similar length (ca. 1 μm) to the seeds, as
revealed by scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) imaging (Figures
2a-p and S4-8). The thickening was found to occur along the
entire nanotube seed (even using multimicrometer long seeds
as shown in Figure S9). Furthermore, the volume difference
between the scroll-like 3D structures and nanotube seeds from
PDI 3 (equal to the diameter squared difference between the
scroll-like 3D structures and nanotube seeds) was linearly
dependent on the molar ratio of microribbons from PDI 1 to
prefabricated nanotubes from PDI
3 (in 1:15 (v/v)
chloroform/ethanol, -50 ℃, 1 h) and microribbons from PDI
4 (in ethanol at -50 ℃ for 10 minutes) and aging for
2
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10.1002/chem.201903066
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the seeds (Figure 2q). Notably, the growth of monomers at the
sides of seeds rather than epitaxial elongation at the termini is
rare for soft matter,[7] and is unprecedented for small molecule
building blocks.
Figure 2. (a) Schematic illustration of the formation of the thickening scroll-like nanostructures. (b-k) SEM, TEM images and
magnified images of the scroll-like nanostructures formed when molar ratio of microribbons from PDI 1 to seeds from PDI 3 was 1:1
(b-d), 2:1 (e-g), 3:1 (h-j), 6:1 (k-m), 10:1 (n-p), respectively. The lengths of the scroll-like nanostructures were in the range of 0.2-1.2
μm, and the dispersities were the same as those of seeds. (q) Linear dependence of volume difference between the scroll-like
nanostructures and seeds from PDI 3 on the N (microribbons from PDI 1)/N (seeds from PDI 3). D = diameter. Error bars, standard
deviation of measured volume difference.
3
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To obtain further insight into the formation of the scroll-like
3D structures, the time-dependent seeded self-assembly of
PDI 1 induced by the addition of nanotube seeds was
monitored by SEM and TEM. As shown in Figure S10, in the
early stages of the seeded self-assembly process, the
metastable microribbons from PDI 1 and the nanotube seeds
from PDI 3 (molar ratio, 1:1) coexisted (Figure S10a). Over
time, the nanotube seeds thicken and the microribbons from
PDI 1 simultaneously became fewer in number and smaller,
indicating that the released monomer PDI 1 from the
disassembly of the metastable microribbons nucleated and
grew on the entire side of the nanotube seeds (Figure S10b-d).
After 7 d, the metastable microribbons disappeared and
substantially thickened three-dimensional scroll-like
structures formed (Figures 2b-d and S10e). Intriguingly, the
peripheral regions on the seeds comprising deposited PDI 1
involved some grooves (Figure 2b-p). The formed grooves
were likely a result of the nonuniform rate of nucleation and
growth of monomer PDI 1 on the entire side of the nanotube
seeds from PDI 3. To clarify that the seeded growth occurred
in the solution phase rather than during solvent evaporation,
the process was investigated by confocal laser scanning
fluorescence microscopy (CLSFM). As shown in Figure
S11a-c, the fluorescence images of the samples in solution
showed that the diameter of the resulting structures increased
with increasing number of microribbons from PDI 1,
confirming seeded growth in the solution phase. Furthermore,
the similar fluorescence spectra of these thickened structures
and the nanotube seeds suggested that the resulting scroll-like
assembly of PDI 1 shared the similar molecular packing with
the nanotube seed from PDI 3 (Figure S11d-f). This was
further supported by XRD results where the XRD pattern of
scroll-like structures was consistent with that of the nanotube
seeds from PDI 3 (Figure S12). As expected, these
fluorescence spectra and XRD patterns differed from those of
PDI 1 nanocoils formed by the unseeded self-assembly
process (Figures S11g-h and S12a). Such a crystal packing
match is consistent with a heteroepitaxial growth mechanism
that allows the nanotube seeds to initiate the growth of
monomer PDI 1 on the periphery. Significantly, the formation
of the scroll-like morphology demonstrates that molecular
species are able to bypass the high energy barrier to access
normally inaccessible self-assembly pathways by using
seeded heteroepitaxial growth.
Given that we have previously demonstrated that the
nanotube seeds from PDI 3 remain active to the addition of
monomer PDI 3, yielding the epitaxial elongated nanotubes at
one terminus,[35] we expected that the sequential addition of
the metastable microribbons from PDIs 1 and 3 would enable
the formation of complex hierarchical assemblies. To this end,
we first prepared the scroll-like 3D structures by adding the
nanotube seeds from PDI 3 in 1:15 (v/v) chloroform/ethanol
to the ten times molar amount of prefabricated stock solution
of microribbons from PDI 1 in 1:15 (v/v) chloroform/ethanol
followed by fully mixing and aging for 1 month (Figure S8).
TEM analysis showed that the resulting scroll-like 3D
structures had diameters of ca. 180-200 nm, similar to those
in Figure 2o-p, and these were used as the seeds for
subsequent self-assembly. Upon addition of the scroll-like
seeds into the prefabricated metastable microribbons from
PDI 3 (Figure S13) in 1:15 (v/v) chloroform/ethanol, the
seeded self-assembly proceeded without intervention for 45 d
and was then analyzed by SEM and TEM. Intriguingly,
Typha-like hierarchical structures were formed (Figure 3a),
where the added PDI 3 epitaxially grew from one terminus of
the parent nanotube seed from PDI 3 (Figure 3b-e and S14).
The non-centrosymmetric growth of PDI 3 induced by the
scroll-like seeds is presumably associated with the molecular
organization within the latter which allows a less steric
hindrance environment on one terminus for growth. The
spatially resolved fluorescence spectra by CLSFM showed
that the elongated nanotube and the scroll-like 3D seeds
exhibited similar spectra, in which only a very small red-shift
emission was observed due to the thickening of the tube
(Figure 3f, g). Once again this is consistent with the similar
molecular packing in the entire Typha-like hierarchical
structure.
Figure 3. (a) Schematic illustration of the formation of the Typha-like nanostructures. (b) SEM image of the Typha-like nanostructures.
(c) Magnified image of the Typha-like nanostructure in (b). (d) TEM image of a Typha-like nanostructure. (e) Magnified image of the
Typha-like nanostructure in (d). (f) Fluorescence image of the Typha-like nanostructure. (g) Fluorescence spectra of the circled areas
1-3 in (f).
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PDI 1, we used microribbon seeds from PDI 4 (Figure S3) as
the initiator. Following the same protocol of addition of
microribbon seeds from PDI 4 in ethanol to the prefabricated
stock solution of microribbons from PDI 1 in 1:15 (v/v)
chloroform/ethanol followed by fully mixing and aging for 30
d, hierarchical scarf-like structures were formed, where the
added PDI 1 grew as tassel nanoribbons from two termini
(Figures 4a-c and S15). The formation of nanoribbon
morphology from PDI 1, which is different from the
morphology of nanocoils in the unseeded self-assembly
process (Figure S1a-b), indicates that an alternative hidden
self-assembly pathway with a high energy barrier exists. The
microribbon seeds from PDI 4 should share similar crystal
packing with the nanoribbons from PDI 1 at both termini and
thereby can minimize the nucleation barrier of PDI 1 toward
the growth. CLSFM characterization revealed that the
fluorescence spectra of the grown nanoribbons were similar to
that of the microribbon seed from PDI 4 regardless of their
distinct morphology (Figures 4d, e and S16), indicative of the
similar crystal packing of these nanoribbons to the
microribbon seeds. XRD measurements also demonstrated
that the scarf-like structures shared the similar molecular
packing to the microribbon seeds (Figures S12 and 17). This
observation, together with the observed growth of PDI 1 from
the side of nanotube seed, demonstrate that the same small
molecule (PDI 1) possesses multiple hidden self-assembly
pathways that can be accessed using different hetero-seeds to
yield unprecedented a range of complex, hierarchical
assemblies.
Figure 4. (a) Schematic illustration of the formation of the scarf-
like nanostructure. (b) SEM image of the scarf-like
nanostructures. (c) Magnified image of a scarf-like nanostructure
in (b). (d) Fluorescence image of a scarf-like nanostructure. (e)
Fluorescence spectra of the circled areas 1 and 2 in (d).
The growth of PDI 1 using microribbon seeds of PDI 4.
To further explore other hidden self-assembly pathways of
Figure 5. (a) Schematic illustration of the formation of the tubular heterostructures. (b) SEM image of seeds from 3 obtained through
ultrasonication. Inset: length distribution of seeds (the lengths of more than 100 nanotubes were measured). (c, d) SEM images of the
tubular heterostructures formed when molar ratio of microribbons from PDI 2 to seeds from PDI 3 was 1:1 (c), 5:1 (d), respectively.
Insets: length distribution of the formed tubular heterostructures (more than 100 tubular heterostructures were measured). Note that the
scale of the x-axis increases from c to d. (e) Linear dependence of the length of tubular heterostructures on the N (microribbons from
PDI 2)/N (seeds from PDI 3). Error bars, standard deviation of measured length. (f) TEM image of the tubular heterostructures in (c).
(g) Magnified image of a tubular heterostructure in (f). (h) Fluorescence image of tubular heterostructures. (i) Fluorescence spectra of
the circled areas 1 and 2 in (h).
5
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Seeded growth of PDI 2. To further explore the influence
building blocks and relevant explorations are underway. It is
also noteworthy that the resulting PDI assemblies are of
interest as electroctive materials as a result of the π-conjugated
of subtle structural modifications on the accessible self-
15, 35-36]
assembly pathways,[13,
we investigated the hetero-
seeded self-assembly of molecule PDI 2 that bears isopropoxy building blocks and detailed studies of their photophysical
group at the 2-position of the phenyl moiety (Figure 1c). In
previous work, we demonstrated the formation of nanocoils of
PDI 2 from the termini of microribbon seeds of PDI 4.[34]
Unseeded self-assembly of 2 yielded a similar nanocoil
morphology from metastable ribbons (Figures 1b and S18)
which indicated that the same pathway was followed under
both sets of conditions. In contrast, seeded growth of PDI 2 in
1:15 (v/v) chloroform/ethanol using nanotube seeds from PDI
3 in 1:15 (v/v) chloroform/ethanol that have lengths ranging
from 0.2 to 1.2 μm (Figure 5b) enabled the nucleation at one
terminus of the nanotube seed and epitaxial growth into the
nanotubular structure (Figures 5 and S19). The non-
centrosymmetric growth behavior of nanotubular structure
can be explained by the fact that distinct exposed surface and
orientation on either terminus of the nanotube seed give
different steric hindrance environment and thereby enables the
preferential nucleation and growth of the upcoming
monomers on one terminus rather than the other. Furthermore,
the length of the elongated nanotube was linearly dependent
on the molar ratio of microribbons from PDI 2 to the nanotube
seeds (Figure 5b-e), suggesting the living growth of 2 on the
end of seeds from PDI 3. A closer examination of TEM
images revealed that the grown tubular segment from 2 had a
smaller diameter compared to the seed segment (Figures 5f, g
and S19e). The formation of the nanotube morphology from
PDI 2, which is different from the nanocoil morphology
formed in the unseeded self-assembly process (Figure S18),
indicates that the self-assembly of PDI 2 to nanotubes is a
hidden pathway. Spatially resolved CLSFM spectra (Figures
5h, i and S11e-f) and XRD patterns (Figures S12 and 20)
showed that the structure of the elongated nanotubes was
similar to that of the nanotube seeds from PDI 3. As expected,
the XRD result of tubular heterostructures (Figure S20b) was
differed from that of the nanocoils from PDI 2 formed by the
unseeded self-assembly process (Figure S20a). On further
decrease of the size of the substituents at the 2-position of the
phenyl moiety to a methoxy group, as in PDI 5 (Figure 1c),
fast self-nucleation and growth into microribbons (Figure S21)
dominated the self-assembly process and no seeded growth of
PDI 5 was observed (Figures S22 and 23). These observations
clearly indicate that the competition between intermolecular
interactions encoded in the molecular structure defines the
energy landscape, including the existence of hidden pathways
with a high energy barrier that cannot be easily accessed.
properties also form part of our future work.
Supporting Information
Supporting Information is available from the Wiley Online
Library or from the author.
Acknowledgements
This work was supported by the NSFC (Nos. 21577147,
21521062, and 21590811) and the “Strategic Priority
Research Program” of the CAS (No. XDA09030200), “Key
Research Program of Frontier Sciences” (No. QYZDY-
SSW-SLH028) of the Chinese Academy of Sciences. I.M.
thanks the Canadian Government for a C150 Research Chair
and the University of Bristol for support.
Conflict of Interest
The authors declare no competing financial interests.
Keywords
hidden self-assembly pathways, hetero-seeding, hierarchical
structures, perylenediimide-based molecules
Received: ((will be filled in by the editorial staff))
Revised: ((will be filled in by the editorial staff))
Published online: ((will be filled in by the editorial staff))
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This article is protected by copyright. All rights reserved.

10.1002/chem.201903066
Chemistry - A European Journal
The table of contents entry: The use of a hetero-seeded growth approach for a series of perylenediimide-
based molecules (PDIs 1 - 4) to access otherwise inaccessible self-assembly pathways that yield complex
hierarchical structures. A nanotube seed (from PDI 3) and a microribbon seed (from PDI 4) were found to
initiate different self-assembly pathways for PDI 1, which normally assembles to yield nanocoils. This led to
the formation of unprecedented 3D scroll-like and scarf-like hierarchical nanostructures, respectively. Also,
the hetero-seeds from PDI 3 initiate hidden self-assembly pathways of PDI 2 to generate 1D tubular
heterojunctions.
Authors: Yin Liu, Yanjun Gong, Yongxian Guo, Wei Xiong, Yifan Zhang,* Jincai Zhao, Yanke Che,* and
Ian Manners
Title: Emergent Self-assembly Pathways to Multidimensional Hierarchical Assemblies via a Hetero-seeding
Approach
8
This article is protected by copyright. All rights reserved.