Reinforced Topological Nanoassemblies: 2D Hexagon-Fused Wheel to 3D Prismatic Metallo-Lamellar Structure with Molecular Weight of 119 K Daltons

Article abstract of DOI:10.1021/jacs.0c00754

By a precise metallo-ligand design, the advanced coordination-driven self-assembly could succeed in the preparation of giant molecular weight of the metallo-architectures. However, the synthesis of a single discrete high-molecular-weight (>100 K Da) struc

Full text of DOI:10.1021/jacs.0c00754

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Article
Reinforced Topological Nano-assemblies: 2D Hexagon-Fused Wheel to 3D
Prismatic Metallo-lamellar Structure with Molecular Weight of 119K Daltons
Guotao Wang, Mingzhao Chen, Jun Wang, Zhilong Jiang, Die Liu, Dongyang Lou, He
Zhao, Kaixiu Li, Suqing Li, Tun Wu, Zhilong Jiang, Xiaoyi Sun, and Pingshan Wang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c00754 • Publication Date (Web): 25 Mar 2020
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Reinforced Topological Nano-assemblies: 2D Hexagon-Fused Wheel
to 3D Prismatic Metallo-lamellar Structure with Molecular Weight of
119K Daltons
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Guotao Wang,†,# Mingzhao Chen,*,‡,# Jun Wang,† Zhiyuan Jiang,† Die Liu,‡ Dongyang Lou,† He Zhao,†
Kaixiu Li,† Suqing Li,† Tun Wu,‡ Zhilong Jiang,‡ Xiaoyi Sun† and Pingshan Wang*,†,‡
†Department of Organic and Polymer Chemistry; Hunan Key Laboratory of Micro & Nano Materials Interface Science,
College of Chemistry and Chemical Engineering; Central South University, Changsha, Hunan-410083, China
‡Institute of Environmental Research at Greater Bay Area; Key Laboratory for Water Quality and Conservation of the
Pearl River Delta, Ministry of Education; Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou Uni-
versity, Guangzhou-510006, China
Self-Assembly • Synthetic metallo-Wheel and Prism • Terpyridine • Topological Molecule
ABSTRACT: By the precisely metallo-ligand design, the advanced coordination-driven self-assembly could succeed the prep-
aration of giant molecular weight of the metallo-architectures. However, the synthesis of single discrete high-molecular-
weight (>100K Da) structure has not been demonstrated since the insurmountable synthetic challenge. Herein we present a
two-dimensional wheel structure (W1) and a gigantic three-dimensional dodecagonal prism-like architecture (P1) which
were generated by multicomponent self-assembly of two similar metallo-organic ligands and a core ligand with metal ions,
respectively. The giant 2D-supra-structure W1 with six hexagonal metallacycles that fused to the central spoke-wheel was
first achieved in nearly quantitative yield, then directed by introducing a meta-substituted coordination site into the key lig-
and, the supercharged (36 Ru2+ and 48 Cd2+ ions) double-decker prismatic structure P1 with two wheel structures W1 serve
as the surfaces and twelve <Tpy-Cd2+-Tpy> connectivities serve as the edges, which possesses a molecular weight up to
119498.18 Da was accomplished. The expected molecular composition and size morphology was unequivocally characterized
by nuclear magnetic resonance, mass spectrometry and transmission electron microscopy investigations. The introduction
of wheel structure is able to add considerable stability and complexity to the final architecture. These well-defined scaffolds
were expected to play an important role in the functional materials fields, such as molecular encapsulation and medicine
sustained-release.
been widely investigated.42-46 However, synthesis of rein-
forced 2D spoke-wheel macromolecules and gigantic 3D
INTRODUCTION
Self-assembly is universal in nature to lead gigantic bio-
logical systems with high-level gracefulness and functional-
ity.1-2 Chemists in various fields are often pushed forward to
think on the artificial synthesis of novel nanoscale-molecu-
lar objects, including nanoparticle assemblies,3-4 self-as-
sembled nanocages,5-14 mechanomolecules,15-19 two-dimen-
sional ensembles,20-25 and so on.26-28 More importantly,
these entities have been employed extensively in the area of
nanoelectronics, sensors, catalysis, supramolecular gels, bi-
ology etc.29-34 Of particular interest in synthetic chemistry is
the discrete two-dimensional (2D) and three-dimensional
(3D) rigid structures, which are accessed by covalent-di-
rected synthesis35-36 and coordination-driven self-assem-
bly37-38 via predesigned rigid precursors. Large molecular
spoked wheels as reinforced macrocycles, which are much
more rigid and stable than the macrocyclic structures, have
received significant attention in the materials field.39-41 On
the other hand, inspired by the function of proteins often in-
timately rely on their sophisticated tertiary spatial struc-
tures, various 3D architectures with different cavity sizes
and shapes are recognized as a promising simulator have
molecular mimics still remains immensely challenging, es-
pecially the covalent methodology has its own synthetic
limitation in the field of reinforced topological architec-
tures.47
Coordination-driven self-assembly, which utilizes the
spontaneous ordering of precursor components into higher
order architectures through the metal-ligand coordination
has proven to be a versatile method for constructing dis-
crete rigid structures.48-52 In stark contrast to the multistep
construction process of covalent approaches, wheel-based
two-dimensional and three-dimensional supramolecules
have been achieved in a one-pot reaction in nearly quanti-
tative yield via supramolecular coordination-driven self-as-
sembly.53-55 Nonetheless, when supramolecular wheels
reach to the next generation, the precise control over their
shape and size faces severe limitations in many instances,
especially for the shape-persistent architectures with size
more than 10 nm. By effectively employing linear terpyri-
dine-metal-terpyridine (tpy-M(Ⅱ)-tpy) coordination as a
dynamic linker, a multitude of higher-order supramolecular
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Figure 1. (A) Illustration of the supramolecularly reinforced architectures: from a rigid spoked wheel to reinforced wheel scaffold
(W1) and further to 3D double-decker dodecagonal prism-like architecture (P1); Structures of (B) W1 and (C) P1.
structures could been achieved by multivalent terpyridine
RESULTS AND DISCUSSION
ligands with various transition metals.56-59
Conventionally, giant terpyridine-based architectures
Herein, we present a supramolecularly reinforced 2D
have been self-assembled by combination of single multiva-
hexagon-fused macromolecule W1 and a 3D supercharged
lent ligand or multiple components with transition metals.
prismatic lamellar structure P1 that been prepared by mul-
No matter which approach is taken, the ligand design is ex-
ticomponent self-assembly of two similar metallo-organic
tremely crucial. For instance, Li et al. employed terpyridine
ligands (LA and LB, respectively) and a core ligand (LH)
and pyrylium salts to prepare octo-topic ligand with differ-
with metal ions (Scheme 1). In reinforced wheel W1, it is
ence in arm length, underwent self-assembly to generate a
self-evident that six hexagonal metallacycles are fused to
ring-in-ring-in-ring-in-ring metal complex with molecular
the central spoke-wheel in two-dimensional plane. The dou-
weight 38,352 Da.61 To create desirable supramolecularly
ble-decker structure P1 exhibits two reinforced wheel W1
reinforced large shape-persistent structures, we designed
in the layers and twelve <Tpy-Cd2+-Tpy> connectivities in
two intricate wing-like metalloorganic ligands LA and LB
the edges which could lead to a dodecagonal prism-like ar-
that consist of three different starting components con-
chitecture (Figure 1). Overall, the giant structure with 168
nected by metal Ru2+ chelation (Scheme 1). We overcome
anions contains 36 Ru2+ and 48 Cd2+ ions with a molecular
the challenge by introducing “Trident” component into the
weight up to 119498.18 Da. Still more interesting is the fact
building block for the first time, which can be perfectly re-
that the discrete supermolecule with such a huge skeleton
acted together with organic ligand LH to generate the antic-
and high molecular weight has not, to the best of our
ipated core wheel, and it is worth mentioning that LH has
knowledge, been specifically documented.60 The super-
been used to build the first generation of spoked wheel.53
charged entity would be expected to give researchers an in-
Moreover, the introduction of meta-substituted coordina-
sight into complicated intermolecular interactions and the
tion site in the key metallo-organic ligand LB could ensure
reinforcement strategy affords elegant way to next genera-
non-planar directionality.62
tion supramolecules and materials.
Self-Assembly and Characterization of the Rigid Scaf-
fold Spoked Wheel W1. In our synthetic design, the
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Scheme 1. (A) Synthesis of Metallo-organic Ligands LA and LB; (B) Self-Assembly of Hexagon-Fused Wheel W1; (C)
Self-Assembly of Prismatic Lamellar Structure P1a
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aReagents and conditions: (i) N-ethyl morpholine, CH3OH:CHCl3 (1:1, v:v), reflux, 1d; (ii, iii) N-ethyl morpholine, CH3OH:CHCl3 (1:1,
v:v), reflux, 1d; (iv, v) Pd(PPh3)4, K2CO3, CH3CN:CH3OH (5:1, v:v), reflux, 5d or 7d; (vi, vii) CH3CN/CHCl3/CH3OH (2:1:1, v:v:v), reflux,
1d.
organic ligands 2, 6, LH were synthesized by known proce-
dures27,54 and the RuIII-terpyridine mono-complexes 1 and 4
were obtained by a multi-step reaction (Scheme S1 and S3).
The key complex 3 was synthesized by reacting 1 with 2
with an isolating process. It is worth noting that 1 is a new-
type promising building block for a diversity of reinforced
wheel structures. The metalloorganic ligand LA was
obtained in three steps from 1. In the final step, a five-fold
Suzuki coupling reaction of the pentabromo-substituted
trinuclear Ru(II) complex 5 with 4’-(4-boronophenyl)-
terpyridine 6 (Scheme 1) was conducted. After refluxing for
5 days under nitrogen at 85 °C, the crude product was
purified by method of flash column chromatography (Al2O3),
and eluting with CH2Cl2 and CH3OH to give metallo-organic
ligand LA. Full experimental details were available in the
supplementary information.
m/z 682.71, 875.87, 1164.80, and 1646.68, in accordance
with the charge states of 6+ to 3+ due to the loss of the cor-
responding number of NTf2− units.
With this metalloorganic ligand LA in hand, we utilized it
as an outer rim, by mixing it with the core ligand LH and
Zn(II) ions at a precise stoichiometric ratio of 6:1:18 for 12
h. Addition of excess bistrifluoromethanesulfonimide lith-
−
ium salt (LiNTf2) as counterion to change NO3 anion to
NTf2− anion, a red precipitate was obtained in nearly quan-
titative yield (94%). This assembled product still showed
good solubility in acetonitrile, N,N-Dimethylformamide and
other solvents. Using acetonitrile as solvent, NMR and elec-
trospray ionization mass spectrometry (ESI-MS) were con-
ducted to determine the molecular composition of the
formed complex.
Figure 2 shows the comparison of 1H NMR spectra of lig-
ands LA, LH and assembled product, all distinguishable
peaks showing that a discrete structure is formed. The
broadening of the peaks is due to the eight different chemi-
cal environments of terpyridine units, and the slow tum-
bling motion on the NMR time scale supporting the for-
mation of a very large complex.63 The evidence for the reac-
tion among ligands and metal ions is that the uncomplexed
terpyridine units in ligands LA and LH witnessed significant
upfield shifts (Δδ > 1.00 ppm). In addition, in the nonaro-
matic region, only a singlet peak at 3.36 ppm for −OCH3 was
observed, which indicated that a single and symmetrical
complex was generated (Figure 2B). The other NMR peak
1
The H NMR spectrum of metalloorganic ligand LA was
complicated owing to the presence of seven chemical envi-
ronments (terpyridine in different environments have been
labeled by letter assignments A to G in order to distinguish
1
their difference, Figure 2). Fortunately, the H NMR spec-
trum exhibited clear sharpening peaks in the expected ratio,
suggesting that the ligand LA was synthesized correctly
(Figure 2A). All the peak assignments of metalloorganic lig-
and LA were further confirmed according to 2D COSY and
2D NOESY NMR (Figures S26 and S27). In addition, the high-
resolution ESI-MS analysis was done to confirm the for-
mation of ligand LA (Figure S62), which displayed peaks at
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Figure 2. NMR study of the hexagon-fused wheel W1. 1H NMR spectra (500 MHz, 298 K) of (A) Metallo-organic ligand LA in CD3CN;
(B) Macromolecule W1 in CD3CN; (C) Organic ligand LH in CDCl3. Methoxy region was assigned to indicated the single -OCH3; (D)
DOSY NMR spectra of reinforced wheel W1 in CD3CN at 25 ˚C. (Terpyridine in different chemical environments were labeled by letter
assignments A-H in order to distinguish their difference)
Figure 3. (A) ESI-MS spectrum and (B) 2D ESI-TWIM-MS plot of hexagon-fused wheel W1; (C) TEM image and the magnified image
of a single W1.
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assignments are confirmed on the basis of the 2D COSY and complex 3. Terpyridine boronic acid 9 was redesigned to in-
1
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4
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8
2D NOESY NMR spectra. 2D NMR diffusion-ordered NMR
spectroscopy (DOSY) was also performed to verify the pu-
rity and size of the macromolecules. There only exists a sin-
troduce methyl- group to increase the solubility of the final
metalloorganic ligand and assembled product. In the final
step, a seven-fold Suzuki coupling reaction of complex 8
with 9 (Scheme 1) was implemented for 7 days using
[Pd(PPh3)4] as the catalyst, the crude product was purified
by method of flash column chromatography (Al2O3). Full
experimental details were available in the supplementary
information.
1
gle band corresponding to the H NMR signal peaks, sug-
gesting that only one species exists in the solution (Figure
2D). Furthermore, the experimental diffusion coefficient (D)
was determined to be 8.31 × 10−11 m2s−1 in CD3CN at 298 K.
Calculated by a modified Stokes-Einstein equation based on
flat structures, the radius (r) of the hexagon-fused wheel
macromolecules was roughly estimated (Supporting Infor-
mation), which exhibiting a relatively smaller size possibly
caused by the broad NMR signal, but confirming that only
one species exist in the solution.
The 1H NMR spectrum of metalloorganic ligand LB is pre-
sented in Figure 4A. There are eight kinds of terpyridine
chemical environments in LB (which have been labeled by
letter assignments A to H in Figure S42) leading to several
overlapping peaks, nevertheless, the expected ratio of the
clear peaks indicates the successful synthesis of ligand LB.
The nonaromatic region displays three singlets at 3.97, 3.94
and 3.21 ppm with 1:1:1 integration ratio corresponding to
the protons of -OCH3. All other assignments of LB protons
were correctly assigned according to 2D COSY and 2D
NOESY spectra (Figures S43 and S44). The composition of
LB was further confirmed by ESI-MS analysis, which exhib-
ited peaks at m/z 877.69, 1109.17 and 1456.39 correspond-
ing to the charge states of 6+ to 4+ due to the loss of the cor-
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Electrospray ionization mass spectrometry (ESI-MS) ex-
periments combined with traveling wave ion mobility mass
spectrometry (TWIM-MS) were performed to further inves-
tigate the composition and purity of accepted supra-
molecule.64 After directly conducting electrospray ioniza-
tion mass spectrometry (ESI-MS), no peaks of zig-zag 1D ol-
igomer which might generate from metalloorganic ligand
LA or organic ligand LH were found, which provided evi-
dence of the quantitative formation of hexagon-fused wheel
W1. The ESI-MS spectrum of W1 exhibiting a series of peaks
derived from the 21+ to 36+ ions (Figure 3A), which was
due to the loss of the corresponding number of NTf2− units
in the ionization process, and their m/z values were con-
sistent with the theoretically calculated values of W1. The
ESI-TWIM-MS spectrum of W1 showed one narrow drift
time distribution ranging from 26+ to 38+ charge states
(Figure 3B), indicating that the desired product possesses
high structural rigidity, as well no isomers exists. Moreover,
when the concentration increases from 0.3 to 5 mg mL-1, the
ESI-MS spectrum revealed that a new series of prominent
peaks appeared near the previous peaks corresponding to
[W1+(CH3CN)n] (n=4, 8, 12), which result from the incorpo-
ration of CH3CN solvent molecules on its surface or coordi-
nation sites65-66 (Figure S70).
−
responding number of NTf2 units, and the experimental
m/z values were completely consistent with the theoretical
ones of LB (Figure S67).
Treating metalloorganic ligand LB with the core ligand
LH in the presence of Cd(NO3)2·4H2O at a precise stoichio-
metric ratio of 6:1:24 gave a clear and transparent solution.
After the solution cooled at room temperature, excess
According to the giant and rigid two-dimensional plane,
transmission electron microscopy (TEM) experiment was
performed to visualize the morphology of individual surpa-
molecules. The reinforced wheel W1 was dissolved in
CH3CN at a concentration of ∼10−6 M and drop-casted on a
carbon-coated copper grid (Cu, 400 mesh) surface. In high-
magnification TEM imaging, the hexagonal-shaped mor-
phology was observed (Figure 3C). The experimental diam-
eters were 13.7± 0.4 nm, which correspond to the theoreti-
cal value of molecular modeling. Moreover, compared with
the outer six hollow hexagons, the central wheels were ob-
served as expected darker dots, the size of those central
dark cores was also consistent with the molecular wheel
(Figure S74).
Figure 4. NMR study of the double-decker dodecagonal prism-
like architecture P1. H NMR spectra (500 MHz, 298 K) of (A)
Self-Assembly and Characterization of the Rigid 3D
Double-Decker Dodecagonal Prism-Like Architecture
P1. Comparison with the metalloorganic ligand LA, the syn-
thetic routes for metalloorganic ligand LB need more elab-
orate design. First, RuIII-terpyridine mono-complex 7
(Scheme 1) that contains bromine and iodine was rede-
signed by bringing a phenyl spacer in meta-substituted po-
sition (Scheme S2). Then, the bromo- and iodo-substituted
Ru2+-complex 8 was obtained based on the same core
1
Metallo-organic ligand LB in DMSO-d6; (B) Double-decker do-
decagonal prism-like architecture P1 in DMSO-d6/CD3CN (1:2);
(C) Organic ligand LH in CDCl3; Methoxy region was assigned
to indicated the single -OCH3; (D) DOSY NMR spectra of rein-
forced wheel P1 in DMSO-d6/CD3CN (1:2) at 25 ˚C. (Terpyri-
dine labeled by letter assignments A-I is provided in the Sup-
porting Information)
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Figure 5. (A) ESI-MS spectrum and (B) 2D ESI-TWIM-MS plot of double-decker dodecagonal prism-like architecture P1; (C) TEM
image and the magnified image of a single P1.
−
−
LiNTf2 in CH3OH was added to exchange NO3 to NTf2 and
obtained a red precipitate. Differing from the reinforced
wheel W1, the giant supramolecular dodecagonal prism-
like architecture P1 obtained here was shown to be poor
solubility in acetonitrile. Especially, when ligands self-as-
sembled with Zn2+, the product became insoluble possibly
due to the weaker reversibility of Zn-based architecture. In-
itial analysis on the final assembly was conducted by NMR
by using the mixture solvent of dimethyl sulfoxide-d6
(DMSO-d6) and CD3CN. Similarly, the broad NMR signals of
P1 suggests the formation of a huge architecture (Figure
4B). It is worth mentioning that the methoxy region shows
three singlets at 4.04, 3.99 and 3.33 ppm with a 1:1:1 ratio
corresponding to the protons of -OCH3, and they were simi-
lar to those for LB, indicating the obtained assembly was a
single and symmetrical complex. All other protons were fur-
ther assigned based on 2D COSY and NOESY spectra (Fig-
ures S53 and S54). In addition, only one single band was
found in the 2D DOSY NMR spectrum of P1 (Figure 4D), the
diffusion coefficient D= 4.26 × 10−11 m2s−1 in CD3CN/d6-
DMSO (1:2) at 298 K, and its calculated radius was 7.3 nm
also confirming that only one species in the solution
(DMSO/CH3CN).
from 34+ to 54+ due to the successive loss of NTf2− anions.
After calculation and analysis, the experimental mass of P1
was calculated with average of 119,498.18 Da, accorded
with
the
formula
of
[Ru36Cd48C4320H3276N360O72]168+·168(NTf2 ), and their m/z
values were also matched with the theoretically calculated
values. Honestly, the molecular weight of the present study
is difficult to obtain a clear isotopic pattern owing to the im-
mense molecular weight and the incorporation of DMF sol-
vent molecules on its surface or coordination sites (Figure
S71). Furthermore, the TWIM-MS spectrum of P1 displayed
signal ranging from 37+ to 50+ charge states with one nar-
row drift time distribution, indicating that there was no iso-
mers or conformers exists (Figure 5B).
−
Transmission electron microscopy experiment was also
performed to provide a powerful evidence for the sizes and
shapes of P1. The TEM image obtained by dissolving P1 in
DMF/CH3CN (∼10−6 M) and drop-casting onto carbon-
coated copper grids (400 mesh) is presented in Figure 5C.
Eight dots with hexagonal-shaped morphology were ob-
served and the averaged calculated diameters was 13.9±
0.4 nm (Figure 5C), agreed well with the diameter of P1 by
modeling (Figure S75).
Most importantly, it is fortunate that the high accuracy of
Waters Synapt G2i Mass Spectrometer is able to provide de-
finitive structural information of such a high molecular
weight assembly. The assembly P1 was dissolved in dime-
thylformamide (DMF) at a concentration of 1 mg mL-1, its
mass spectrometry data is presented in Figure 5A, which
display a series of peaks corresponding to the charge states
CONCLUSIONS
In summary, we expanded supramolecular self-assembly
strategy toward a reinforced hexagon-fused wheel and a 3D
gigantic three-dimensional dodecagonal prism-like archi-
tecture with molecular weights up to 47 KDa and 119 KDa,
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(6) Chakrabarty, R.; Mukherjee, P. S.; Stang, P. J., Supramolecular
coordination: self-assembly of finite two- and three-dimensional
ensembles. Chem. Rev. 2011, 111 (11), 6810-6918.
respectively, which may be difficult to access by taking ad-
1
2
3
4
5
6
7
8
vantages of other approaches. By employing stepwise syn-
thesized metallo-organic ligands that containing trident
component replace the simple rim building block, such gi-
ant nano-assemblies were obtained by a reinforcement
strategy. The high-molecular-weight structures are remi-
niscent of biological macromolecules such as typical pro-
teins and protein assemblies.67-68 1D and 2D NMR, High-res-
olution MS analysis and TEM investigation were imple-
mented to unambiguously support the expected molecular
composition and size morphology. Like the two-dimen-
sional covalent organic framework and metal organic
framework materials, those stable supramolecular struc-
tures with well-defined geometries are expected to play an
important role in the functional materials fields.69-70 This
work exemplifies the potential of coordination assembly to
synthesize large and sophisticated architectures and devel-
ops the reach of supramolecular coordination systems into
biomimetic science.
(7) Ahmad, N.; Chughtai, A. H.; Younus, H. A.; Verpoort, F.,
Discrete metal-carboxylate self-assembled cages: Design, synthesis
and applications. Coordin. Chem. Rev. 2014, 280, 1-27.
(8) Smulders, M. M.; Riddell, I. A.; Browne, C.; Nitschke, J. R.,
Building on architectural principles for three-dimensional
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at http://pubs.acs.org at DOI. Exper-
imental procedures and characterization data, including 1H, 13C,
COSY, NOESY, and DOSY spectra of the new compounds and
ESI-MS spectra of related compounds (PDF)
AUTHOR INFORMATION
Corresponding Author
* M. Chen: jinyulinzhao@foxmail.com
* P. Wang: chemwps@csu.edu.cn
ACKNOWLEDGMENT
We acknowledge the support from National Natural Science
Foundation of China (21971257) and Hunan Provincial Science
and Technology Plan Project of China (No. 2019TP1001). The
authors gratefully acknowledge the Center for Advanced Re-
search in CSU for the NMR measurements.
(18) Wilson, M. R.; Sola, J.; Carlone, A.; Goldup, S. M.; Lebrasseur,
N.; Leigh, D. A., An autonomous chemically fuelled small-molecule
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synthesis of molecular knots. Chem. Soc. Rev. 2013, 42 (4), 1700-
1712.
ORCID
Pingshan Wang: 0000-0002-1988-7604
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molecular assemblies
supramolecular chemistry. Chem. Soc. Rev. 2013, 42 (4), 1713-
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(22) Marquis, A.; Kintzinger, J. P.; Graff, R.; Baxter, P. N. W.; Lehn,
J.-M., Mechanistic Features, Cooperativity, and Robustness in the
- macrocyclic complexes in metallo-
Author Contributions
#G.W. and M.C. contributed equally to this work.
Notes
The authors declare no competing financial interest.
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Reinforced Topological Nano-assemblies: 2D Hexagon-Fused Wheel to 3D Prismatic Metallo-lamellar Struc-
ture with Molecular Weight of 119K Daltons
Guotao Wang, Mingzhao Chen, Jun Wang, Zhiyuan Jiang, Die Liu, Dongyang Lou, He Zhao, Kaixiu Li, Suqing Li, Tun Wu,
Zhilong Jiang, Xiaoyi Sun and Pingshan Wang
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