Controlled Hierarchical Self-Assembly of Catenated Cages

Article abstract of DOI:10.1021/jacs.0c03330

Constructing hierarchical superstructures to achieve comparable complexity and functions to proteins with four-level hierarchy is challenging, which relies on the elaboration of novel building blocks with complex structures. We present a series of catenated cages with unique structural complexity and tailorability. The rational design was realized as such: A catenane of two symmetric cages (CSC), CSC-1, with all rigid imine panels was converted to a catenane of two dissymmetric cages (CDC), CDC-1, with two exterior flexible amine panels, and CDC-5 was tailored from CDC-1 by introducing an additional methyl group on each blade to increase lateral hindrance. CDC-1s with the most irregular and flexible configuration formed supramolecular dimers, which self-organized into 3D continuous wavelike plank with a three-level hierarchy, previously undiscovered by conventional building blocks. A drastically different 3D triclinic crystalline phase with a four-level hierarchy and trigonal phase with a three-level hierarchy were constructed of distorted CSC-1s and the most symmetric CDC-5s, respectively. The wavelike plank exhibited the lowest order, and the triclinic phase had a lower order than the trigonal phase which had the highest order. It correlates with the configuration of the primary structures, namely, the most disordered shape of CDC-1, the low-order configuration of CSC-1, and the most ordered geometry of CDC-5. The catenated cages with subtle structural differences therefore provide a promising platform for the search of emerging hierarchical superstructures that might be applied to proton conductivity, ferroelectricity, and catalysis.

Full text of DOI:10.1021/jacs.0c03330

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Article
Controlled Hierarchical Self-Assembly of Catenated Cages
Zhongwei Sun, Pan Li, Shijun Xu, Zi-Ying Li, Yoshiaki Nomura, Zimu Li, Xiaoyun Liu, and Shaodong Zhang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c03330 • Publication Date (Web): 20 May 2020
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Controlled Hierarchical Self-Assembly of Catenated Cages
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Zhongwei Sun,†,ǂ Pan Li,†,ǂ Shijun Xu,‡ Zi-Ying Li,‡ Yoshiaki Nomura,† Zimu Li,† Xiaoyun Liu,‡ and
Shaodong Zhang*,†
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†School of Chemistry and Chemical Engineering, Frontiers Science Centre for Transformative Molecules,
Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, 800
Dongchuan Road, Shanghai 200240, China.
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‡Key Laboratory of Specially Functional Polymeric Materials and Related Technology (ECUST), Ministry
of Education, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237,
China.
ABSTRACT: Constructing hierarchical superstructures to achieve comparable complexity and functions
to proteins with four-level hierarchy is challenging, which relies on the elaboration of novel building blocks
with complex structures. We present a series of catenated cages with unique structural complexity and
tailorablity. The rational design was realized as such: CSC-1 with all rigid imine panels was converted to
CDC-1 with two exterior flexible amine panels, and CDC-5 was tailored from CDC-1 by introducing an
additional methyl group on each blade to increase lateral hindrance. CDC-1s with the most irregular and
flexible configuration form supramolecular dimers, which self-organize into 3D continuous wave-like
plank with three-level hierarchy, precedently undiscovered by conventional building blocks. Drastically
different 3D triclinic crystalline phase with four-level hierarchy and trigonal phase with three-level
hierarchy were constructed by distorted CSC-1s and the most symmetric CDC-5s, respectively. The wave-
like plank exhibits the lowest order, and the triclinic phase has a lower order than the trigonal phase with
the highest order. It correlates with the configuration of the primary structures, namely the most disordered
shape of CDC-1, low-order configuration of CSC-1, and the most ordered geometry of CDC-5. The
catenated cages with subtle structural differences therefore provide a promising platform for the search of
emerging hierarchical superstructures that might be applied to proton conductivity, ferroelectricity, and
catalysis.
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INTRODUCTION
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First proposed by Linderstrøm-Lang,1 hierarchical structures of proteins with four levels, namely primary,
secondary, tertiary and quaternary structures, have been well-documented to play a pivotal role in biological
functions of living systems.2 Inspired by the wisdom of nature, synthetic hierarchical structures have been
developed with a large variety of building blocks and applied to biomimetics,3 electronics,4 and catalysis.5
Synthetic systems, however, were still unable to reach the parallel structural sophistication and functions
as proteins. This challenge can be addressed by increasing the complexity of existing building blocks6 or
searching for novel candidates.7 Considering the 3D topological diversity of cage- or capsule-like
compounds,8 they could be one type of promising building blocks. For more than two decades, research
focus has been mainly dedicated to the design, synthesis and applications.9 Awareness of their potential as
powerful synthons for hierarchical superstructures has been raised only very recently.10 Among these cage-
like molecules, catenated (or interlocked) cages composed of two or more monomeric cages,11 particularly
covalent catenated cages pioneered by Cooper, Mastalerz, Zhang, Sessler and Li,12 have attracted increasing
interest due to their aesthetic structures and potential applications. On the basis of the unique three-
dimensional and complex topology, self-assembly of catenated cages might provide a powerful toolbox for
the discovery of hierarchical superstructures that are inaccessible by conventional molecules and cages, but
it remains underexplored.13
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We herein present a series of catenated cages, which were rationally designed with unique structural
complexity and tailorability. Starting from a catenane composed of two symmetric cages, denoted CSC-1,
we converted it to the corresponding catenane composed of two dissymmetric cages, CDC-1 (Figure 1).
As CDC-1 exhibits two exterior amine panels (in red), more structural flexiblity is implanted with respect
to CSC-1 with four rigid imine panels (in blue). We also tailored CDC-1 by introducing an additional
methyl group on each dithiane moiety, yielding CDC-5 with more steric hindrance on its periphery. More
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importantly, we demonstrate that these catenated cage with subtle structural differences can self-assemble
in a controlled hierarchical manner, leading to dramatically different superstructures. These hierarchical
superstructures include: an unprecedented 3D continuous wave-like plank with three-level hierarchy, which
was previously inaccessible by conventional building blocks; a 3D triclinic crystalline with four clearly
defined levels of structure, which is close to the four-level hierarchy of proteins; a 3D trigonal crystalline
with three-level hierarchy, which exhibits the highest order compared to other two superstructures. As such,
a small structural modification of the catenated cages alters dramatically their topological configurations,
which in turn results in substantially different hierarchical superstructures. The structural effect of catenated
cages on their configurations and hierarchical self-assembly behaviors in crystal state is also elaborated in
this work.
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Figure 1. Rational design of catenated cages for hierarchical self-assembly. Compared to CSC-1 with four
relatively rigid imine panels, CDC-1 with two exterior amine panels exhibits higher configurational
flexibility. With one extra methyl group (highlighted in green) on each dithiane moiety, CDC-5 has higher
lateral hindrance than CDC-1. The amine panels are shown in red, and imine panels in blue.
RESULTS AND DISSCUSSION
Synthesis and Characterization of Catenated Cages. We previously developed a synthetic strategy
to construct catenane with two dissymmetric cages (denoted CDC).14 We started from the catenane
composed of two symmetric cages, namely CSC-1. As the inner cavity of CSC-1 is inaccessible by
voluminous NaBH(OAc)3, it allowed us to selectively reduce all imines on its exterior panels, leading to
the formation of CDC-1. Similarly, CDC-5 was produced by a two-step procedure. [4+6] cycloimination
of four TFB panels and six (4R)-2-(3,5-di(3-aminophenyl)phenyl)-4-methyl-1,3-dithiane (DAPMD)
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linkers first yielded CSC-5. The subsequent selective reduction of the exterior imines of CSC-5 by bulky
reductant NaBH(OAc)3 led to the formation of CDC-5 (44% two-step overall yield, see Supporting
Information for details). Its chemical structure was confirmed by MALDI-TOF and NMR spectroscopies,
respectively (Figures S8-S12). The MALDI-TOF spectrum of CDC-5 shows an ion peak at m/z 2799.936
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([M+H]+ calcd for 2799.927), and its H NMR spectrum exhibits the resonances related to the exterior
amine bonds (protons Hb’ and Hn’), the interior imine bonds (proton Hs’), TFB (protons Ha’ and Hr’), and
two sets of DAPMD (typically protons Hc’-Hf’ vs. protons Hj’-Hm’), respectively.
Figure 2. Molecular structures of catenated cages CSC-1, CDC-1 and CDC-5. (a, c, e) Top view in space-
filling and (b, d, f) side view in stick modes of the catenated cages, respectively. They are dissected into
two monomeric cages for easy inspection of their configurations, including their rotation and twisting. The
exterior amine panels are shown in red, interior imine panels in blue, lateral linkers in light/dark grey to
differentiate the two interlocked partner cages. Methyl groups in CDC-5 are highlighted in green. Curved
arrows show the rotating direction of the blades, and straight arrows indicate the swaying direction of
dithiane rings. Solvent molecules and hydrogen atoms are omitted for clarity.
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Molecular Configurations of Catenated Cages in Crystalline State. Single crystals suitable for X-
ray crystallography were obtained by slow vapor diffusion of diethyl ether into concentrated THF solution
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of CSC-1,14 slow evaporation from the saturated solutions of CDC-1 in THF and CDC-5 in CH3CN/THF
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= 2:5 v/v at 35 ºC, respectively. CSC-1 crystallized into triclinic space group
, CDC-1 into monoclinic
푃1
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space group C2/c, and CDC-5 into trigonal space group R32. Their molecular configurations were
unambiguously inspected by dissecting them into two partner cages (Figure 2).
CSC-1 exhibits a fairly irregular propeller-like configuration. Its top view shows the three m-terphenyl
blades of each partner cage exhibit different rotating directions (Figure 2a). Its side view reveals its four
relatively rigid imine panels (in blue) are aligned nearly parallel to each other (Figure 2b). Their parallel
packing with close distances (3.6, 3.7 and 3.6 Å) ensures efficient intramolecular π-π stacking, which
provides, to some extent, ridigity of CSC-1 during crystallization. Besides, all the dithiane rings are
swaying in different directions. CDC-1 with two flexible amine panels (in red) adopts a very disordered
shape without any element of symmetry. Its top view shows three m-terphenyl blades of one partner cage
(in dark grey) simultaneously rotate clockwise, while the three blades of another cage (in light grey) are
irregularly twisted (Figure 2c). This highly disordered geometry is also apparent from its side view (Figure
2d). The exterior amine panel (in red) of each partner cage is notably distorted. This leads to uneven
distribution of centroid distances between four panels, i.e., 4.1, 3.8, and 3.8 Å. It therefore precludes
efficient intramolecular π-π stacking between the exterior amine panels (in red) and the adjacent interior
imine panels (in blue) of CDC-1. Similar to CSC-1, all dithiane rings of CDC-1 exhibit different swaying
fashion. CDC-5 with one additional methyl group on each blade exhibits a highly symmetric configuration
with one C3-symmetric axis and three perpendicular C2-symmetric axes. Its top view reveals all three blades
of each partner cage rotating in the same direction (Figure 2e), and the side view shows its four panels are
aligned parallel to each other (Figure 2f). Their close distances (3.8, 3.6 and 3.8 Å) and parallel packing
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also ensure efficient intramolecular π-π stacking, which favors the ordered interlocking of the two partner
cages.
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Comparison of these catenated cages therefore clearly shows their subtle structural changes, namely
CSC-1 with more rigid imine panels vs. CDC-1 with two flexible amine panels, and CDC-5 with flexible
amine panels but laterally bulkier vs. CDC-1, dramatically alters their topological configurations in
crystalline state. It leads to the most disordered and flexible configuration for CDC-1, fairly irregular shape
for CSC-1, and highly symmetrical geometry for CDC-5 in crystalline state. It is noteworthing the
structural tailoring can also be realized with the homologous simple cages, but imine-to-amine conversion
often leads to the collapse of their crystal structures.15 This structure-to-configuration correlation therefore
demonstrates the unique structural feature of our catenated cages.
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3D Hhierarchical Structures Self-Assembled by Catenated Cages. It is worth noting that all these
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three catenated cages adopt highly symmetrical geometries in solution, as revealed by their H NMR
splitting patterns determined in CDCl3 (Figure S8).14 The irregular configurations of CSC-1 and CDC-1 in
crystal state seemly result from their dense packing during crystallization, which requires considerable
distortion so that the void in crystals is minimized. As the configuration of a molecule and its self-assembly
behavior, i.e., molecular packing, are interdependent during crystallization,16 it prompted us to investigate
the self-assembly of CSC-1, CDC-1 and CDC-5 in crystalline state, respectively.
CSC-1 exhibits a fairly irregular propeller-like shape with all blades twisting differently, but with four
imine panels (in blue) aligned in parallel (Figures 2a, 2b, and 3b). As revealed by a combination of structural
and retrostructural analysis (Figures 3),17 CSC-1 molecules self-assemble into triclinic crystalline phase
via controlled hierarchy with well-defined primary, secondary, tertiary, and quaternary structures. This is
reminiscent of the hierarchical self-assembly of polypeptides into proteins.2a
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Figure 3. Controlled hierarchical self-assembly of CSC-1s into 3D triclinic crystalline phase with well-
defined primary, secondary, tertiary, and quaternary structures. (a) Stick mode of primary structure CSC-
1. (b) Supramolecular dimer (secondary structure) self-assembled by CSC-1s. Dashed arrows through
CSC-1s indicate their opposite orientations. (c) Staggered helical column (tertiary structure) formed by
supramolecular dimers. The simplified cartoon model (right) of four CSC-1s (two dimers) showing their
intermolecular arrangement with detailed packing parameters. Two neighbouring CSC-1s with opposite
orientation are arranged off the columnar axis (in yellow), around which each CSC-1 rotates by 180º with
respect to another. (d) Quaternary structures self-organized by supramolecular columns, viewed along
crystallographic a- (left) and c-axis (right), respectively. The imine panels are in blue. Light/dark grey on
lateral linkers and cartoon model of each CSC-1 is to differentiate the two interlocked monomeric cages.
Solvent molecules and hydrogen atoms are omitted for clarity.
Two CSC-1s (primary structures) aggregate into a supramolecular dimer within a unit cell, in which
one CSC-1 molecule adopts the opposite orientation with respect to another, as illustrated by the dashed
arrows placed through CSC-1s (Figure 3b). Besides, these two CSC-1s are offset by 9.6 Å. This packing
therefore impedes intermolecular π-π stacking between the imine panels (in blue) of adjacent CSC-1s. The
parallel alignment of the four panels of a CSC-1 is therefore maintained only by intramolecular π-π stacking
(vide supra). These dimers (secondary structures) are packed to form a staggered helical column (tertiary
structure, Figure 3c). The simplified cartoon model of the column clearly illustrates their intermolecular
arrangement (right panel in Figure 3c). Two neighbouring CSC-1s with opposite orientation are arranged
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off the columnar axis (in yellow), around which each CSC-1 rotates by 180º with respect to another. Such
arrangement leads to the formation of a 21-helix with a pitch of 29.0 Å. Besides, every two adjacent
molecules are offset by 3.4 Å along the columnar axis. These supramolecular columns self-organize into
3D quaternary supramolecular structure, with a center-to-center distance of 18.3 Å (Figure 3d).
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Figure 4. Controlled hierarchical self-assembly of CDC-1s into 3D continuous wave-like plank with well-
defined primary, secondary, and tertiary structures. (a) Stick mode of primary structure CDC-1. (b)
Supramolecular dimer (secondary structure) self-assembled by CDC-1s. Dashed arrows through CDC-1
indicate their opposite orientations. (c) Tertiary structure self-organized by supramolecular dimers (upper
panel). This packing is illustrated with a simplified model of tiling of bricks in a zig-zag fashion (bottom
panel). Each supramolecular dimer “brick” is labeled in blue or orange to distinguish dimers with different
orientation, and deep and light colors tell different layers of “bricks”. The exterior amine panels are shown
in red, interior imine panels in blue. Lateral linkers are in light/dark grey to differentiate the two interlocked
monomeric cages. Solvent molecules and hydrogen atoms are omitted for clarity.
CDC-1 molecules with the most disordered and flexible configuration crystallize into the hierarchical
superstructure of monoclinic crystalline phase with well-defined primary, secondary, and tertiary structures
(Figures 4). The primary structures, i.e., CDC-1s also self-assemble into a supramolecular dimer. Similar
to the case of CSC-1s, within the dimer the two CDC-1 molecules adopt opposite orientation with respect
to each other, as illustrated by the dashed arrows placed through CDC-1s (Figure 4b). Besides, the two
CDC-1s are offset by 9.4 Å. This packing also precludes intermolecular π-π stacking between the amine
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panels (in red) of adjacent CDC-1s. Along with the absence of efficient intramolecular π-π stacking (vide
supra), it leads to the distortion of the exterior amine panels of CDC-1s (Figures 4b). These dimers, serving
as secondary building blocks, self-organize into a strikingly special superstructure in a wave-like manner,
which we refer to as 3D continuous wave-like plank (Figure 4c). This unique packing is reminiscent of
tiling of bricks, which is illustrated and self-explanatory with two representative layers of planks, assembled
with the “bricks” (simplified model for supramolecular dimers) in a zig-zag fashion (bottom panel in Figure
4c). Each supramolecular “brick” is labeled in blue or orange, respectively, to distinguish dimers with
different orientations. Besides, two layers of “bricks” with an offset of 6.8 Å are differentiated with deep
and light colors. As illustrated by Figure S16, the seemingly energetically unfavourable zig-zag is stablized
by both edge-to-face packing (along crystallographic c-axis) and face-to-face packing (along b-axis) of the
adjcent dimer “bricks”, leading to a tight packing of CDC-1 molecules in the crystalline phase.
To the best of knowledge, this novel hierarchical superstructure has not been discovered by
conventional self-assembling building blocks. The highly irregular and adaptable geometry of CDC-1s
(with flexible exterior amine panels and with less steric hindrance on the periphery, Figure 4a) seemly plays
a key role in such unusual and inefficient packing. This structure-to-superstructure correlation might
provide a guideline for the design of similar building blocks for the search of novel supramolecular
structures in the future.
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CDC-5 is a tailored version of CDC-1, with one extra methyl group on each blade, and its self-
assembly is dramatically altered (Figure 5). Highly symmetrical CDC-5 molecules with a radius of 14.3 Å
aggregate into the trigonal crystalline phase (Figure 5a). The structural and retrostructural analysis of this
supramolecular structure reveals that CDC-5s self-asssemble in a controlled hierarchical manner as well.
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Figure 5. Controlled hierarchical self-assembly of CDC-5 into 3D trigonal crystalline phase with well-
defined primary, secondary, and tertiary structures. (a) Stick mode of primary structure CDC-5. (b)
Supramolecular column (secondary structure) self-assembled by CDC-5s. The red dashed circle highlights
alignment of dithiane rings, and the enlarged image shows distance between two CDC-5s. (c) Tertiary
structure with columnar crystalline hexagonal lattice self-organized by supramolecular columns, with
colors distinguishing different columns. Upper panel shows three representative columns viewed along
crystallographic b-axis, with the inset showing detailed packing parameters. Bottom panel shows the
packing of columns viewed along c-axis, with the enlarged image revealing the dithiane rings are
interwoven with each other (yellow dashed rectangle) between neighbouring CDC-5s. Solvent molecules
and hydrogen atoms are omitted for clarity.
CDC-5s, serving as primary structures, are packed into supramolecular columns (Figure 5b). In each
column CDC-5s are perfectly superimposed with each other, with an intermolecular distance of 3.8 Å (side
view in Figure 5b). This packing facilitates effective intermolecular π-π stacking between the exterior amine
panels (in red) of adjacent CDC-5s. Along with the intramolecular π-π stacking (vide supra), it favors the
ordered alignment of all panels of a CDC-5, and ensures its symmetric configuration during crystallization.
Besides, every dithiane ring is tilted and aligned with its homologues of other CDC-5s along the column
axis, as highlighted by red dashed circle (tilt view in Figure 5b). These columns (secondary structures),
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self-organize into tertiary 3D supramolecular structure (Figure 5c). They are labelled with different colors
for easy analysis. Along crystallographic b-axis, three representative columns are aligned in parallel with a
center-to-center distance of 19.5 Å and an average vertical offset of 4.9 Å (upper panel in Figure 5c). The
dithiane rings are staggered evenly with distance of 4.0 Å. When viewed along c-axis, each column is
packed with six columns, forming a columnar hexagonal lattice (bottom panel in Figure 5c). As the diameter
of each CDC-5 is 28.6 Å (Figure 5a), which is larger than the center-to-center distance of 19.5 Å of two
columns, the dithiane rings are therefore interwoven with each other between the neighbouring CDC-5s,
as highlighted by yellow dashed rectangles. Along with the vertical offset mentioned above, CDC-5s adopt
such packing pattern where these erstwhile bulky dithiane moieties are hosted within the intercolumnar
channels, so as to avoid their steric hindrance yet ensure tight packing of CDC-5 molecules. This packing
also seemly facilitates the maintenance of the highly symmetric configuration of CDC-5 during crystal
formation. It is also worth noting that CDC-5s exhibit the most regular configuration among the three
catenate cages in the current study, which aggregate to form the 3D superstructure with the highest order.
Structural Effect on Topological Configuration and Self-Assembly Behaviour of Catenated
Cages. As mentioned above, the structural tailoring of these catenated cages was realized as follows: CSC-
1 with all rigid imine panels vs. CDC-1 with two flexible amine panels, and CDC-5 with flexible exterior
amine panels but laterally bulkier vs. CDC-1. CSC-1 adopts a fairly irregular propeller-like shape, but the
relatively rigid imine bonds help to maintain the parallel alignment of its four panels. They self-assemble
into supramolecular dimers, and the dimers form low-order helical columns, which self-organize into the
3D triclinic crystalline with four clearly defined levels of structure. Two flexible exterior amine panels and
less hindered periphery of CDC-1 favor the highly irregular distortion. It facilitates the self-assembly of
CDC-1s into brick-like supramolecular dimers, which self-organize into the unusual 3D wave-like plank
in a zig-zag fashion (the lowest order). Compared to CDC-1s, extra methyl groups on the periphery of
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CDC-5s urge the interweaving of their dithiane rings during the self-assembly, which is beneficial to
maintain their most symmetric propeller-like geometry. They self-assemble into perfect supramolecular
columns, which self-organize into the 3D trigonal crystalline with the highest order. The order of the
triclinic crystalline phase is lower than that of the trigonal crystalline phase, which results from the
difference between the low-order configuration of CSC-1 and the high-order geometry of CDC-5. It
therefore demonstrates that subtle structural change of catenated cages alters dramatically their topological
configurations, which in turn leads to their different hierarchical self-assembly behaviors. Although the
symmetric molecules are generally believed to form the most thermodynamically favored polymorphs
during self-assembly, the influence of solvent cannot be overlooked. The complexation of these catenated
cages with various solvents during crystallization is currently under investigation in our laboratories.
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CONCLUSIONS
In conclusion, we prepared various 3D superstructures by self-assembly of a series of catenated cages in a
controlled hierarchical manner. Our study reveals that catenated cages provide a promising molecular
platform, which allows us to seek hierarchical superstructures that are inaccessible for conventional self-
assembling building blocks and simple cages, such as 3D wave-like plank self-assembled by CDC-1
presented in this work. This unusual packing pattern is attributed to the highly distorted topology and
configurational flexibility of CDC-1. Three different hierarchical superstructures were achieved with subtle
structural modification of our catenated cages, and it therefore highlights the advantage of their tailorablity.
These superstructures could be used for the discovery of emerging materials with unusual properties.
For example, the Connolly surface analyses of these superstructures (Figure S13) reveal that potential
porous channels can be constructed by the controlled hierarchical self-assembly of our catenated cages to
form various types of extrinsic voids. Along with the strategy of our selective post-modification—not
limited to the reduction—of the external panels of an symmetric catenated cage, it will open up new
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opportunities for exploring chirality manipulation, proton conductivity, ferroelectricity, catalysis, and so
on, which are the ongoing endeavours within our laboratories.
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Supporting Information
The Supporting Information is available free of charge at on the ACS Publications website.
Characterization methods, experimental details and characterization of compounds (PDF)
Crystal structure for CSC-1 (CIF)
Crystal structure for CDC-1 (CIF)
Crystal structure for CDC-5 (CIF)
AUTHOR INFORMATION
Corresponding Author
Shaodong Zhang − School of Chemistry and Chemical Engineering, Frontiers Science Centre for
Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai
Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China; orcid.org/0000-0001-7923-8457;
Email: sdzhang@sjtu.edu.cn.
Authors
Zhongwei Sun − School of Chemistry and Chemical Engineering, Frontiers Science Centre for
Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai
Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
Pan Li − School of Chemistry and Chemical Engineering, Frontiers Science Centre for Transformative
Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong
University, 800 Dongchuan Road, Shanghai 200240, China; orcid.org/0000-0003-0901-003X
Shijun Xu − Key Laboratory of Specially Functional Polymeric Materials and Related Technology
(ECUST), Ministry of Education, East China University of Science and Technology, 130 Meilong Road,
Shanghai 200237, China; orcid.org/0000-0002-7102-6561
Zi-Ying Li − Key Laboratory of Specially Functional Polymeric Materials and Related Technology
(ECUST), Ministry of Education, East China University of Science and Technology, 130 Meilong Road,
Shanghai 200237, China; orcid.org/0000-0002-6443-492X
Yoshiaki Nomura − School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University,
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800 Dongchuan Road, Shanghai 200240, China
Zimu Li − School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800
Dongchuan Road, Shanghai 200240, China
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Xiaoyun Liu − Key Laboratory of Specially Functional Polymeric Materials and Related Technology
(ECUST), Ministry of Education, East China University of Science and Technology, 130 Meilong Road,
Shanghai 200237, China; orcid.org/0000-0002-9838-1109
Author Contributions
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ǂZ.S. and P.L. contributed equally.
Notes
The authors declare no competing interests.
ACKNOWLEDGMENTS
This work was supported by National Natural Science Foundation of China (key program 21890733), and
the Shanghai Natural Science Foundation (18ZR1420800). We thank Dr. Hang Wang (MALDI-TOF MS)
and Wanping Lu (Supercritical Fluid Chromatography) at the Instrumental Analysis Centre of SJTU, and
Rongrong Yu for his assistance in chiral HPLC characterization. We thank Dr. Shan Jiang from
ShanghaiTech University for constructive discussion and suggestions.
ABBREVIATIONS
CSC, Catenane of symmetric cages; CDC, Catenane of dissymmetric cages.
REFERENCES
(1) Linderstrøm-Lang, K. U. Lane Medical Lectures: Proteins and enzymes. Stanford Univ. Publ. Med.
Series. 1952, 6, 1–115.
(2) (a) Sibanda, B. L.; Thornton, J. M. β-Hairpin Families in Globular Proteins. Nature 1985, 316, 170–
174; (b) Whitesides, G. M.; Grzybowski, B. Self-Assembly at All Scales. Science 2002, 295, 2418–2421.
(3) (a) Yadavalli, S. S.; Xiao, Q.; Sherman, S. E.; Hasley, W. D.; Klein, M. L.; Goulian, M.; Percec, V.
Bioactive Cell-like Hybrids from Dendrimersomes with a Human Cell Membrane and its Components.
Proc. Natl. Acad. Sci. U. S. A. 2019, 116, 744–752; (b) Rodriguez-Emmenegger, C.; Xiao, Q,; Kostina, N.
Y.; Sherman, S. E.; Rahimi, K.; Partridge, B. E.; Li, S.; Sahoo, D.; Reveron Perez, A. M.; Buzzacchera, I.;
Han, H.; Kerzner, M.; Malhotra, I.; Möller, M.; Wilson, C. J.; Good, M. C.; Goulian, M.; Baumgart, T.;
14
ACS Paragon Plus Environment

Page 15 of 19
1
Journal of the American Chemical Society
Klein, M. L.; Percec, V. Encoding Biological Recognition in a Bicomponent Cell-membrane Mimic. Proc.
Natl. Acad. Sci. U. S. A. 2019, 116, 5376–5382; (c) Sherman, S. E.; Xiao, Q.; Percec, V. Mimicking
Complex Biological Membranes and their Programmable Glycan Ligands with Dendrimersomes and
Glycodendrimersomes. Chem. Rev. 2017, 117, 6538–6631.
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(4) (a) Chen, L.; Mali, K. S.; Puniredd, S. R.; Baumgarten, M.; Parvez, K. Pisula, W.; De Feyter, S.; Müllen,
K. Assembly and Fiber Formation of a Gemini-Type Hexathienocoronene Amphiphile for Electrical
Conduction. J. Am. Chem. Soc. 2013, 135, 13531−13537; (b) Nickmans, K.; Schenning, A. P. H. J. Directed
Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning. Adv. Mater.
2018, 30, 1703713.
(5) (a) Wu, S.; Li, Y.; Xie, S.; Ma, C.; Lim, J.; Zhao, J.; Kim, D. S.; Yang, M.; Yoon, D. K.; Lee, M.; Kim,
S. O.; Huang, Z. Supramolecular Nanotubules as a Catalytic Regulator for Palladium Cations: Applications
in Selective Catalysis. Angew. Chem. Int. Ed. 2017, 56, 11511–11514; (b) Shen, Z.; Sang, Y.; Wang, T.;
Jiang, J.; Meng, Y.; Jiang, Y.; Okuro, K.; Aida, T.; Liu, M. Asymmetric Catalysis Mediated by a Mirror
Symmetry-Broken Helical Nanoribbon. Nat. Commun. 2019, 10, 3976.
(6) (a) O’Leary, L. E. R.; Fallas, J. A.; Bakota, E. L.; Kang, M. K.; Hartgerink, J. D. Multi-Hierarchical
Self-Assembly of a Collagen Mimetic Peptide from Triple Helix to Nanofibre and Hydrogel. Nat. Chem.
2011, 3, 821−828; (b) Kim, H.-J.; Liu, F.; Ryu, J.-H.; Kang, S.-K.; Zeng, X.; Ungar, G.; Lee, J.-K.; Zin,
W.-C.; Lee, M. Self-Organization of Bent Rod Molecules into Hexagonally Ordered Vesicular Columns.
J. Am. Chem. Soc. 2012, 134, 13871−13880; (c) Huang, M.; Hsu, C.-H.; Wang, J.; Mei, S.; Dong, X.; Li,
Y.; Li, M.; Liu, H.; Zhang, W.; Aida, T.; Zhang, W.-B.; Yue, K.; Cheng, S. Z. D. Selective Assemblies of
Giant Tetrahedra via Precisely Controlled Positional Interactions. Science 2015, 348, 424−428; (d) Sahoo
D.; Peterca, M.; Aqad, E.; Partridge, B. E.; Heiney, P. A.; Graf, R.; Spiess, H. W.; Zeng, X.; Percec, V.
Hierarchical Self-Organization of Perylene Bisimides into Supramolecular Spheres and Periodic Arrays
Thereof. J. Am. Chem. Soc. 2016, 138, 14798−14807; (e) Kim, K.; Schulze, M. W.; Arora, A.; Lewis III,
R. M.; Hillmyer, M. A.; Dorfman, K. D.; Bates, F. S. Thermal Processing of Diblock Copolymer Melts
Mimics Metallurgy. Science, 2017, 356, 520–523; (f) Holerca, M. N.; Sahoo, D.; Partridge, B. E.; Peterca,
M.; Zeng, X.; Ungar, G.; Percec, V. Dendronized Poly (2-oxazoline) Displays within only Five Monomer
Repeat Units Liquid Quasicrystal, A15 and σ Frank–Kasper phases. J. Am. Chem. Soc. 2018, 140,
16941−16947; (g) Percec, V. Merging Macromolecular and Supramolecular Chemistry into Bioinspired
Synthesis of Complex Systems. Isr. J. Chem. 2020, 60, 48−66.
15
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Page 16 of 19
1
2
3
4
5
6
7
8
(7) (a) Jones, J. T. A.; Hasell, T.; Wu, X.; Bacsa, J.; Jelfs, K. E.; Schmidtmann, M.; Chong, S. Y.; Adams,
D. J.; Trewin, A.; Schiffman, F.; Cora, F.; Slater, B.; Steiner, A.; Day, G. M.; Cooper, A. I. Modular and
Predictable Assembly of Porous Organic Molecular Crystals. Nature 2011, 474, 367–371; (b) Yamagishi,
H.; Sato, H.; Hori, A.; Sato, Y.; Matsuda, R.; Kato, K.; Aida, T. Self-Assembly of Lattices with High
Structural Complexity from a Geometrically Simple Molecule. Science 2018, 361, 1242–1246.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(8) (a) Kang, J.; Rebek, J. Acceleration of a Diels–Alder Reaction by a Self-Assembled Molecular Capsule.
Nature 1997, 385, 50–52; (b) Dalgarno, S. J.; Tucker, S. A.; Bassil, D. B.; Atwood, J. L. Fluorescent Guest
Molecules Report Ordered Inner Phase of Host Capsules in Solution. Science 2005, 309, 2037–2039; (c)
Fujita, M.; Oguro, D.; Miyazawa, M.; Oka, H.; Yamaguchi, K.; Ogura, K. Self-assembly of Ten Molecules
into Nanometre-Sized Organic Host Frameworks. Nature 1995, 378, 469–471; (d) Olenyuk, B.; Whiteford,
J. A.; Fechtenkotter, A.; Stang, P. J. Self-Assembly of Nanoscale Cuboctahedra by Coordination Chemistry.
Nature 1999, 398, 796–799; (e) Brenner, W.; Ronson, T. K.; Nitschke, J. R. Separation and Selective
Formation of Fullerene Adducts within an MII L6 Cage. J. Am. Chem. Soc. 2017, 139, 75−78; (f) Tozawa,
8
T.; Jones, J. T. A.; Swamy, S. I.; Jiang, S.; Adams, D. J.; Shakespeare, S.; Clowes, R.; Bradshaw, D.;
Hasell, T.; Chong, S. Y.; Tang, C.; Thompson, S.; Parker, J.; Trewin, A.; Bacsa, J.; Slawin, A. M. Z.;
Steiner, A.; Cooper, A. I. Porous Organic Cages. Nat. Mater. 2009, 8, 973–978; (g) Zhang, C.-X.; Wang,
Q.; Long, H.; Zhang, W. A. Highly C70 Selective Shape-Persistent Rectangular Prism Constructed
through One-Step Alkyne Metathesis. J. Am. Chem. Soc. 2011, 133, 20995−21001; (h) Beaudoin, D.;
Rominger, F.; Mastalerz, M. Chiral Self‐Sorting of [2+3] Salicylimine Cage Compounds. Angew. Chem.
Int. Ed. 2017, 56, 1244–1248.
(9) (a) Yoshizawa, M.; Tamura, M.; Fujita, M. Diels-Alder in Aqueous Molecular Hosts: Unusual
Regioselectivity and Efficient Catalysis. Science 2006, 312, 251–254; (b) Jin, Y.; Voss, B. A.; Noble, R.
D.; Zhang, W. A Shape‐Persistent Organic Molecular Cage with High Selectivity for The Adsorption of
CO2 over N2. Angew. Chem. Int. Ed. 2010, 49, 6348–6351; (c) Brutschy, M.; Schneider, M. W.; Mastalerz,
M.; Waldvogel, S. R. Porous Organic Cage Compounds as Highly Potent Affinity Materials for Sensing by
Quartz Crystal Microbalances. Adv. Mater. 2012, 24, 6049–6052; (d) Kaphan, D. M.; Levin, M. D.;
Bergman, R. G.; Raymond, K. N.; Toste, F. D. A Supramolecular Microenvironment Strategy for Transition
Metal Catalysis. Science 2015, 350, 1235–1238; (e) Jiao, T.; Chen, L.; Yang, D.; Li, X.; Wu, G.; Zeng, P.;
Zhou, A.; Yin, Q.; Pan, Y.; Wu, B.; Hong, X.; Kong, X.; Lynch, V. M.; Sessler, J. L.; Li, H. Trapping
White Phosphorus within a Purely Organic Molecular Container Produced by Imine Condensation. Angew.
16
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Page 17 of 19
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Journal of the American Chemical Society
Chem. Int. Ed. 2017, 56, 14545–14550; (f) Mondal, B.; Mukherjee, P. S. Cage Encapsulated Gold
Nanoparticles as Heterogeneous Photocatalyst for Facile and Selective Reduction of Nitroarenes to Azo
Compounds. J. Am. Chem. Soc. 2018, 140, 12592−12601; (g) Liu, M.; Zhang, L.; Little, M. A.; Kapil, V.;
Ceriotti, M.; Yang, S.; Ding, L.; Holden, D. L.; Balderas-Xicohténcat, R.; He, D.; Clowes, R.; Chong, S.
Y.; Schütz, G.; Chen, L.; Hirscher, M.; Cooper, A. I. Barely Porous Organic Cages for Hydrogen Isotope
Separation. Science 2019, 366, 613–620; (h) Wang, Y.; Sun, Y.; Shi, P.; Sartin, M. M.; Lin, X.; Zhang, P.;
Fang, H.; Peng, P.; Tian, Z.; Cao, X. Chaperone-like Chiral Cages for Catalyzing Enantio-Selective
Supramolecular Polymerization. Chem. Sci. 2019, 10, 8076–8082; (i) Gao, S.; Yan, X.; Xie, G.; Zhu, M.;
Ju, X.; Stang, P. J.; Tian, Y.; Niu, Z. Membrane Intercalation-Enhanced Photodynamic Inactivation of
Bacteria by a Metallacycle and TAT-Decorated Virus Coat Protein. Proc. Natl. Acad. Sci. USA 2019, 116,
23437–23443.
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(10) (a) Fowler, D. A.; Mossine, A. V.; Beavers, C. M.; Teat, S. J.; Dalgarno, S. J.; Atwood, J. L.
Coordination Polymer Chains of Dimeric Pyrogallol[4]arene Capsules. J. Am. Chem. Soc. 2011, 133,
11069–11071; (b) Zhang, C.; Patil, R. S.; Liu, C.; Barnes, C. L.; Atwood, J. L. Controlled 2D Assembly of
Nickel-Seamed Hexameric Pyrogallol[4]arene Nanocapsules. J. Am. Chem. Soc. 2017, 139, 2920−2923;
(c) Zhang, C.; Wang, F.; Patil, R. S.; Barnes, L. C.; Li, T.; Atwood, J. L. Hierarchical Self‐Assembly of
Supramolecular Coordination Polymers Using Giant Metal–Organic Nanocapsules as Building Blocks.
Chem. Eur. J. 2018, 24, 14335–14340; (d) Thorp-Greenwood, F. L.; Ronson, T. K.; Hardie, M. J. Copper
Coordination Polymers from Cavitand Ligands: Hierarchical Spaces from Cage and Capsule Motifs, and
Other Topologies. Chem. Sci. 2015, 6, 5779–5792; (e) Su, K.; Du, S.; Wang, W.; Yuan, D. Metal-Organic
Cages (MOCs): From Discrete to Cage-Based Extended Architectures. Chem. Lett. 2020, 49, 28–53.
(11) (a) Fujita, M.; Fujita, N.; Ogura, K.; Yamaguchi, K. Spontaneous Assembly of Ten Components into
Two Interlocked, Identical Coordination Cages, Nature 1999, 400, 52–55; (b) Westcott, A.; Fisher, J.;
Harding, L. P.; Rizkallah, P.; Hardie, M. J. Self-Assembly of a 3-D Triply Interlocked Chiral [2]Catenane,
J. Am. Chem. Soc. 2008, 130, 2950–2951; (c) Yamauchi, Y.; Hanaoka, Y.; Yoshizawa, M.; Akita, M.;
Ichikawa, T.; Yoshio, M.; Kato, T.; Fujita, M. m× n Stacks of Discrete Aromatic Stacks in Solution. J. Am.
Chem. Soc. 2010, 132, 9555–9557; (d) Kuang, X.; Wu, X.; Yu, R.; Donahue, J. P.; Huang, J.; Lu, C.-Z.
Assembly of a Metal–Organic Framework by Sextuple Intercatenation of Discrete Adamantane-Like Cages.
Nat. Chem. 2010, 2, 461-465; (e) Löffler, S.; Lübben, J.; Krause, L.; Stalke, D.; Dittrich, B.; Clever, G. H.
Triggered Exchange of Anionic for Neutral Guests Inside a Cationic Coordination Cage. J. Am. Chem. Soc.,
17
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2
3
2015, 137, 1060–1063.
4
5
6
7
8
9
(12) (a) Hasell, T.; Wu, X.; Jones, J. T. A.; Bacsa, J.; Steiner, A.; Mitra, T.; Trewin, A.; Adams, D. J.;
Cooper, A. I. Triply Interlocked Covalent Organic Cages. Nat. Chem. 2010, 2, 750–755; (b) Zhang, G.;
Presly, O.; White, F.; Oppel, I. M.; Mastalerz, M. A. Shape‐Persistent Quadruply Interlocked Giant Cage
Catenane with Two Distinct Pores in the Solid State. Angew. Chem. Int. Ed. 2014, 53, 5126–5130; (c) Wang,
Q.; Yu, C.; Long, H.; Du, Y.; Jin, Y.; Zhang, W. Solution‐Phase Dynamic Assembly of Permanently
Interlocked Aryleneethynylene Cages through Alkyne Metathesis. Angew. Chem. Int. Ed. 2015, 54, 7550–
7554; (d) Li, H.; Zhang, H.; Lammer, A. D.; Wang, M.; Li, X.; Lynch, V. M.; Sessler, J. L. Quantitative
Self-Assembly of a Purely Organic Three-Dimensional Catenane in Water. Nat. Chem. 2015, 7, 1003–
1008.
10
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52
53
54
55
56
57
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(13) Bloch, W. M.; Holstein, J. J.; Dittrich, B.; Hiller, W.; Clever, G. H. Hierarchical Assembly of an
Interlocked M8L16 Container. Angew. Chem., Int. Ed. 2018, 57, 5534−5538.
(14) Li, P.; Xu, S.; Yu, C.; Li, Z.-Y.; Xu, J.; Li, Z.-M.; Zou, L.; Leng, X.; Gao, S.; Liu, Z.; Liu, X.; Zhang,
S. De novo Construction of Catenane of Dissymmetric Cages via Space-Discriminative Post-Assembly
Modification. Angew.Chem. Int.Ed. 2020, 59, 7113–7121.
(15) Jelfs, K. E.; Wu, X.; Schmidtmann, M.; Jones, J. T. A.; Warren, J. E.; Adams, D. J.; Cooper, A. I.
Large Self‐Assembled Chiral Organic Cages: Synthesis, Structure, and Shape Persistence. Angew. Chem.,
Int. Ed. 2011, 50, 10653–10656.
(16) Desiraju, G. R. Supramolecular Synthons in Crystal Engineering—a New Organic Synthesis. Angew.
Chem. Int. Ed. Engl. 1995, 31, 2311–2321.
(17) Sun, H.-J.; Zhang, S.; Percec, V. From Structure to Function via Complex Supramolecular Dendrimer
Systems. Chem. Soc. Rev. 2015, 44, 3900–3923.
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