Based on the principle of geometric complementation and the high “density of coordination sites”, these metalloligands were assembled with Zn2+ ions to form a pinwheel-shaped star trigon
Trang 1Construction of Macromolecular Pinwheels Using Predesigned
Metalloligands
Jun Wang,# He Zhao,# Mingzhao Chen, * Zhiyuan Jiang, Feng Wang, Guotao Wang, Kaixiu Li,
Zhe Zhang, Die Liu, Zhilong Jiang, and Pingshan Wang *
ABSTRACT: Developing a methodology to build target
struc-tures is one of the major themes of synthetic chemistry However,
it has proven to be immensely challenging to achieve multilevel
elaborate molecular architectures in a predictable way Herein, we
describe the self-assembly of a series of pinwheel-shaped starlike
supramolecules through three rationally preorganized
metal-loligands L1−L3 The key octa-uncomplexed terpyridine (tpy)
metalloligand L3, synthesized with an 8-fold Suzuki coupling
reaction to metal-containing complexes, has four different types of
terpyridines connected with three⟨tpy-Ru2+-tpy⟩ units, making this
the most subunits known so far for a preorganized module Based
on the principle of geometric complementation and the high
“density of coordination sites”, these metalloligands were assembled with Zn2+ ions to form a pinwheel-shaped star trigon P1, pentagram P2, and hexagram P3 with precisely controlled shapes in nearly quantitative yields With molecular weights ranging from
16756 to 56053 Da and diameters of 6.7−13.6 nm, the structural composition, shape, and rigidity of these pinwheel-shaped architectures have been fully characterized by 1D and 2D (NMR), electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy
■ INTRODUCTION
Molecular nanotechnology is one strategy for addressing
beauty in molecules.1 Structures of various shapes have been
created over the last few decades.2Significant advances in the
synthesis of beautiful molecular objects at the nanometer scale
have been elegantly realized, including geometric stars,3
self-similar fractals,4 Archimedean polyhedrals,5 mechanically
interlocked objects,6 and others.7 Among these, geometric
star structures are common in nature and art, such as in
multipetalflowers, snowflakes, Star of David, and pinwheels In
addition, pentameric and hexameric cyclic shapes have
symbolic significance in many cultures and religions, such as
the Star of David These well-organized molecular systems can
reach an amazing level of sophistication and functionality in
molecular reactors,8 photonics,9 drug delivery,10 sensing,11
catalysis,12 and other systems.13 For example, Leigh et al
synthesized a pentafoil knot that promotes catalyzed chemical
reactions through the breakage of carbon−halogen bonds and
anion abstraction.14
However, routes to build for the multilevel geometric
structures in a predictable way still remain a challenge
Noncovalent interactions, which are common behaviors in
natural biological systems and can provide access to highly
complex proteins, have inspired chemists to employ
self-assembly to fabricate many types of molecules.15
Coordina-tion-driven self-assembly is an important noncovalent inter-action that has been utilized to construct supramolecular architectures with definite sizes and shapes.16
In the last few decades, Lehn,17 Fujita,18 Stang,19 Leigh,20 Nitschke,21 and others22have reported numerous examples of beautiful 2D and 3D supramolecular architectures using this strategy One N-donor bridging ligand that has received immense attention is 2,2′:6′,2″-terpyridine, which possesses octahedral ⟨tpy-M2+ -tpy⟩ connectivity bound to geometrically oriented ligands.23 Notably, the molecular design of supramolecular architec-tures with definite sizes and shapes essentially relies on the control of angled vectors and the coordination geometry.2b Despite this, it has been proven that the self-assembly process
of extended ligands might not strictly follow their angular direction, which increases the challenge of assembling an ideal single product.24For instance, a mixture of macrocycles (from pentamer to nonamer) was generated in the self-assembly of a ditopic 120° angle ligand with Zn2+, however, discrete hexagon Received: July 25, 2020
© XXXX American Chemical Society https://dx.doi.org/10.1021/jacs.0c08020
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Trang 2wreaths can be achieved by increasing the density of the
coordination sites, which provides the final architectures with
more geometric and rigidity constraints.25Moreover, we have
previously proposed a stepwise strategy for constructing
preblocked metallo-organic ligands to reduce the
fragmenta-tion of thefinal constructs.26
We expected that high generation
of metallosupramolecules might be exclusively produced in a
roundabout way by using multinuclear metalloligands to
increase the terminal coordination sites Note that
pinwheel-shaped compounds in N-donor-based supramolecular
struc-tures have been unknown until now, although the design
principles via coordination-driven self-assembly have been well
understood and employed with high success for the synthesis
of 2D supramolecular polygons
Herein, we present our preparation of different
pinwheel-shaped stellated metallosupramolecules using a rationale
terpyridine-based precursor design Three novel multitopic
metalloligands, L1, L2, and L3, were designed and synthesized
by taking advantage of the inert ⟨tpy-Ru2+-tpy⟩ in a stepwise
manner (Scheme 1) Key metalloligands L1 and L2 with four
uncomplexed free terpyridines are featured in a truncated
rhombus bound to a V-directed tenon They were assembled
with Zn2+ ions to introduce a discrete pinwheel-shaped star
trigon P1 and pentagram P2 (the trimer and pentamer
product, respectively), attributed to the intramolecular
mortise−tenon joint.27
Both P1 and P2 were composed of
rhombuses by utilizing vertex connectivity, and possess a triangle and pentagon, respectively, in the center More importantly, a larger and more complicated pinwheel-shaped hexagram P3 (a hexamer product) could be generated via the coordination of an octaterpyridine metalloligand (L3) and
Zn2+ ions (Scheme 1) These species with rigid pinwheel-shaped architectures possess central symmetry, which may show potential applications in selective catalysis and molecular machines
■ RESULTS AND DISCUSSION
Self-Assembly of Pinwheel-Shaped Star Trigon P1 via Preorganized Metalloligand L1 A multistep route and a final Suzuki-coupling reaction26a
were utilized to synthesize the tetra-uncoordinated metallo-organic ligand L1 Tetrabromo-substituted Ru2+ complex 1 was first obtained by connecting bisterpyridine and two bromo-containing components with two Ru2+metal ions (Scheme S1) Metalloligand L1 with four free terpyridines was achieved through a 4-fold Suzuki-coupling reaction of 4-terpyridinyl-B(OH)2with 1, using Pd0
as the catalyst, K2CO3 as the base, refluxing for 4 days, and purifying by column chromatography (Al2O3) with a mixed
CH2Cl2/CH3OH eluent (Scheme 2) The key bismetallic ligand L1 possesses three types of components that are presented as a truncated rhombus bound to a V-directed tenon
in a 60° orientation
Scheme 1 Self-Assembly of Pinwheel-Shaped Star Trigon, Pentagram, and Hexagram
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Trang 3The 1H NMR spectrum of L1 (Figure 1A) shows two
distinct singlets at 9.20 and 8.99 ppm in a 1:1 ratio, which were
assigned to the H3′,5′protons of the Ru-connected terpyridine;
the other H3′,5′ terpyridine protons overlapped with other
peaks The nonaromatic region displays one multiplet and
three singlets in a 4:3:3:3 ratio attributed to a pair of−OCH2−
protons and three −OCH3 protons, which agrees very well
with the theoretical proportions The other assignments were
fully confirmed with the assistance of homonuclear chemical
shift correlation spectroscopy (COSY), and nuclear
Over-hauser effect spectroscopy (NOESY) (Figures S50−S52)
Moreover, diffusion-ordered spectroscopy (DOSY) was used
to confirm the purity of ligand L1; only one narrow band
corresponding to the 1H NMR spectrum was observed,
confirming the absence of other byproduct (Figure 1B)
Additional evidence for ligand L1 was confirmed by
electro-spray ionization mass spectrometry (ESI−MS) experiments,
which exhibited peaks at m/z 802.51, 1164.64, and 1886.89, in
good agreement with charge states of 4+ to 2+ obtained by
losing NTf2−(Figure S91)
Direct self-assembly was conducted by mixing metalloligand
L1with Zn(NTf2)2in a precise stoichiometric ratio of 1:2 in a
mixed solvent of CH3CN/CH3OH (v/v, 1/1) for 12 h under
reflux After the mixture was cooled to room temperature,
excess LiNTf2 (dissolved in CH3OH) was added and the
mixture was then filtered to obtain a red precipitate In our
original design, we anticipated that the complementarity of the ligand drives the formation of a surrounding rhombus pinwheel-shaped star trigon The resultant assembly was initially identified by1H NMR and ESI−MS, which indicated that the target product P1 was formed in nearly quantitative yield (>95%)
As shown in Figure 1A, in comparison with the 1H NMR spectrum of ligand L1, well-split and similar signals in the nonaromatic region of P1 were observed, indicating the formation of a single and symmetrical complex One multiplet and three singlets at 4.26−4.24, 3.97, 3.94, and 3.16 ppm in a 4:3:3:3 ratio were attributed to a pair of−OCH2− protons and three −OCH3 protons, which only showed small shifts from the −OCH2− and −OCH3groups in L1 (Figure 1A) In the aromatic region, six singlets and one overlapping signal at 9.16, 9.11, 9.08, 9.06, 9.03, 8.93, and 8.87 ppm in a 1:1:2:1:1:1:1 ratio were attributed to the H3′,5′protons of the eight types of terpyridines In addition, all H6,6′′ protons from free terpyridines were characteristically shifted upfield owing to the electron-shielding effects of the metal ions Other
spectra (Figures S2−S4) In comparison with the DOSY spectrum of ligand L1, an increasing diffusion coefficient was observed in P1, which showed narrow bands at log D =−9.60 and −9.75 m2s−1for L1 and P1, respectively (Figure 1B,C), demonstrating the expected size increase from ligand L1 to
Scheme 2 Synthesis of the Rationally Preorganized Metallo-organic Ligands L1−L3a
a Reagents and conditions: (i) Tpy-B(OH)2, Pd(PPh3)4, K2CO3, CH3CN/CH3OH (2/1, v/v), reflux; (ii) N-ethylmorpholine, CH 3 OH/CHCl3(1/
1, v/v), reflux; (iii) RuCl 3 ·3H 2 O, EtOH, reflux; (iv) N-ethylmorpholine, CHCl 3 /CH3OH (3/1, v/v), reflux.
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Trang 4complex P1 In addition, the experimental hydrodynamic
radius (rH) of P1 was 3.3 nm, which was calculated by the
Stocks−Einstein equation and agreed well with the outer radii
derived from the simulated molecular size (∼3.3 nm) The single band in the DOSY spectrum of P1 also confirmed that only one species was present in the solution
Figure 1 NMR study of metallo-organic ligand L1 and star trigon P1: (A) comparison of 1 H NMR (500 MHz, in CD3CN) of L1 (top) and P1 (bottom); (B,C) DOSY NMR spectra (500 MHz, 298 K) of L1 and P1 in CD3CN, respectively.
Figure 2 Mass spectrometry for pinwheel-shaped star trigon P1 and pentagram P2: (A) ESI-MS spectrum and (B) 2D ESI-TWIM-MS plot of P1; (C) ESI-MS spectrum and (D) 2D ESI-TWIM-MS plot of P2 Insets: theoretical and experimental isotopic patterns.
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Trang 5The composition of the assembled supramolecule P1 was
supported by ESI-MS experiments As shown in Figure 2A, a
series of peaks with successive charge states from 16+ to 9+
was observed at m/z 767.04, 836.91, 916.75, 1008.72, 1116.02,
1243.01, 1395.39, and 1581.43, which was due to the loss of
different numbers of NTf2− anions during ionization The
calculated molecular weight exactly matched the desired
structure with a molecular weight of 16756 Da, in accordance
with the formula (Zn6L13)24+(NTf2)24−, and the isotope
patterns for all charge states were consistent with the
corresponding theoretical values of P1 (the detailed isotope
patterns are summarized inFigure S100) Traveling wave ion
mobility mass spectrometry (TWIM-MS) was also used to
investigate the isomeric separation process.28The narrow drift
time distributions for states from 14+ to 10+ indicate the
absence of isomers and oligomers resulting from self-assembly
(Figure 2B)
Self-Assembly of Pinwheel-Shaped Pentagram P2 via
Pre-Organized Metalloligand L2 Subsequently, a similar
metallo-organic ligand L2 with a truncated rhombus bound to
a V-directed tenon in a 120° orientation was designed and
synthesized from the tetrabromo-substituted Ru complex 3
exhibited clean, sharp signal peaks and showed six singlets at
9.08, 9.01, 8.98, 8.89, 8.87, and 8.80 ppm with a 1:1:1:1:1:1
integration ratio attributed to the H3′,5′protons of the six types
of terpyridines; the other two signal peaks of the tpy-H3',5'
protons overlapped with the tpy-H6,6" protons at 8.75−8.73
ppm In the methoxy region, a multiplet andfive singlets were
observed at 4.21−4.18, 3.91, 3.89, 3.28, 3.22, and 3.15 ppm with a 4:3:3:3:3:3 ratio, corresponding to a triplet for
other assignments were fully confirmed with the assistance of 2D COSY and NOESY (Figures S58−S61) Similarly, the DOSY spectrum of L2 displayed one narrow band at log D =
−9.49 m2s−1, suggesting the absence of other byproducts
811.49), 3+ (m/z 1174.95), and 2+ (m/z 1903.35) in the
ESI-MS spectrum also verified the successful synthesis of L2 (Figure S93)
The reaction of L2 with 2 equiv of Zn(NTf2)2in a mixed solvent of CH3CN/CH3OH (v/v, 1/1) at 75 °C for 12 h resulted in the pinwheel-shaped pentagram P2, which was isolated in 95% yield as a red solid after precipitation with excess LiNTf2 in MeOH Both NMR and ESI-MS analyses supported the predicted structure
The 1H NMR signals of P2 were similar to those for L2, which proves the P2 symmetry As shown in Figure 3A, a multiplet and four singlets were observed in the methoxy region at 4.23, 3.99, 3.97, 3.34, and 3.19 ppm with a 7:3:3:3:3 ratio In addition, eight types of tpy-H3′,5′ protons were observed at 9.10, 9.07, 9.04, 9.00, and 8.97 ppm with a 1:2:2:2:1 integration ratio All H6,6′′protons (marked by the dotted lines inFigure 3A) from free terpyridines dramatically shifted upfield owing to electron-shielding effects, which indicate the formation of bistpy−metal coordination All other assignments were successfully confirmed on the basis
of 2D COSY and NOESY spectra (Figures S6−S8) In
Figure 3 NMR study of metallo-organic ligand L2 and pinwheel-shaped pentagram P2: (A) comparison of 1 H NMR (500 MHz, in CD3CN) of L2 (top) and P2 (bottom); (B, C) DOSY NMR spectra (500 MHz, 298 K) of L2 and P2 in CD 3 CN, respectively.
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Trang 6addition, the 2D DOSY spectrum (Figure 3C) of complex P2
showed a distinct narrow band at log D = −9.90 m2 s−1,
indicating the formation of a single discrete product in
CD3CN, with an experimental hydrodynamic radius of 4.7 nm,
which agrees well with the simulated molecular size (∼4.8
nm)
The formula of (Zn10L25)40+(NTf2)40−for P2 was accurately
identified by ESI-MS As shown inFigure 2C, a series of peaks
with continuous charge states (m/z) from 22+ to 11+ was
observed, as indicated by the loss of different numbers of
NTf2− anions; the experimental m/z values and their
corresponding isotope patterns were completely consistent
with the desired P2 structure with a molecular weight of 28088
Da The TWIM-MS plots of P2 displayed a series of narrow
drift time distributions for charge states from 18+ to 11+, and
no plots of oligomer and isomeric structures were found,
indicating that pinwheel-shaped pentagram P2 is a discrete and
rigid product without other structural conformers (Figure 2D)
Self-Assembly of Pinwheel-Shaped Hexagram P3 via
an Octaterpyridine Metalloligand L3 Encouraged by the
successful synthesis of a pinwheel-shaped star trigon and
pentagram, we expected that the pinwheel-shaped hexagrams
could be exclusively produced by increasing the terminal
coordination sites to restrict theflexibility of the metalloligand
An extremely complex metalloligand L3 was designed by
connecting four different organic components with Ru2+
connectors (Scheme S3) To the best of our knowledge,
there is no report on a man-made metallo-organic ligand with
four different components and eight free terpyridines in one
molecule
Structurally, metalloligand L3 contains 14 types of
terpyridines, including six coordinated (three ⟨tpy-Ru2+-tpy⟩
connectors) and eight uncomplexed terpyridines Therefore,
the 1H NMR spectrum of L3 displayed a set of rather
complicated signal peaks owing to its structural asymmetry As
shown in Figure 4A, there were broad peaks in the aromatic region owing to the plentiful peak overlaps derived from the 14 terpyridine environments Fortunately, the1H NMR spectrum showed clear, sharp peaks in the methoxy region One overlapped signal and six distinct signals at 4.01, 3.99, 3.89, 3.23, 3.20, 3.17, and 3.16 ppm with a 1:1:2:1:1:1:1 ratio were observed in the spectrum, which were attributed to the protons
of eight types of −OCH3with the expected ratio All protons were assigned based on 2D COSY and 2D NOESY experiments (Figures S79−S81) In the DOSY spectrum of L3, one narrow band at log D = −9.60 m2s−1was observed, suggesting that only one species was present in the CD2Cl2 solution (Figure 4B) In addition, metalloligand L3 was further analyzed by ESI-MS experiments The ESI-MS spectrum of L3 exhibited a series of peaks from 6+ to 3+ from the loss of the corresponding NTf2−anions (Figure S98), and the calculated molecular weight completely matched the simulated data, confirming the successful synthesis of L3
After mixing metalloligand L3 with 4 equiv of Zn(NTf2)2in
a mixed solvent of CH3CN/CH3OH (v/v, 1/1) at 75°C for
24 h, a red precipitate of P3 was obtained by adding an excess amount of LiNTf2into the assembly solution and precipitating
by deionized water Compared to pinwheel-shaped pentagram P2, hexagram P3 possesses an extra outer constraint, which may break the structural flexibility and provide the metal-loligand with greater rigidity, leading to the assembly preferring the formation of a hexagram rather than a pentagram
ligand L3 and P3, and the same number of terpyridine environments (14) leads to similar complicated peaks Moreover, peaks broader than those in L3 were observed in P3, which also supports the formation of a large product owing
to the slow tumbling motion on the NMR time scale However, the nonaromatic region exhibited two multiplets and three singlets at 4.04, 3.92, 3.33, 3.30, and 3.18 ppm in a
Figure 4 NMR study of metallo-organic ligand L3 and pinwheel-shaped hexagram P3: (A) comparison of 1 H NMR (500 MHz) of L3 in CD2Cl2 (top) and P3 in CD3CN (bottom); (B, C) DOSY NMR spectra (500 MHz, 298 K) of L3 in CD2Cl2and P3 in CD3CN, respectively.
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Trang 72:2:1:1:1 ratio, which were derived from seven −OCH3
protons Another−OCH3proton overlapped with the solvent
peak at 3.25 ppm, which was confirmed by 2D NOESY and 2D
DOSY, and all other assignments were carefully assigned based
on 2D COSY and 2D NOESY spectra (Figures S10−S12)
DOSY was also conducted to test the purity and size of the
pinwheel-shaped hexagram P3 A distinct narrow band at log D
= −10.04 m2s−1corresponding to the 1H NMR signal peaks
also confirmed that only one discrete product was present in
the solution (CD3CN) Along with the increase in the
pinwheel-shaped architecture generation (P1−P3), it was
found that the absolute value of log D was gradually increasing
This expected trend provided indirect support for the
successful synthesis of a larger structure Again, according to
the Stokes−Einstein formula, the experimental hydrodynamic
radius of 6.5 nm was similar to that of the simulated molecular
size (∼6.8 nm)
More evidence for the successful synthesis of
pinwheel-shaped hexagram P3 was provided by the ESI-MS analysis
The ESI-MS spectrum of P3 showed a series of peaks at m/z
1194.50, 1235.07, 1277.08, 1321.60, 1368.94, 1418.77,
1471.93, 1528.36, 1588.73, 1653.13, 1722.01, 1796.08,
1875.95, 1962.24, 2066.67, 2157.11, and 2268.04, which
were obtained by losing successive NTf2− groups and
correspond to charge states from 38+ to 22+ After
deconvolution and analysis, these values corresponded well
w i t h t h e t h e o r e t i c a l v a l u e s o f
[(C326H222N42O8Ru3)6Zn24(C2F6NO4S2)84] with a molecular
weight of 56053 Da (Figure 5) Owing to the very large
molecular weight and the resolution limits of the instrument, it
is difficult to obtain a satisfactory isotopic pattern Two minor
peaks behind each charge state were found, probably from the
ionization of the NTf2− counterions (Figure S103) More
importantly, the TWIM-MS plots of P3 displayed a series of
narrow drift time distributions at charge states from 38+ to
22+, and no plots of oligomer or isomeric structures were
found, suggesting the successful formation of a single discrete assembly
Stability Study of Macromolecular Pinwheels P1−P3
To investigate the stability of P1, P2, and P3, gradient tandem-mass spectrometry (gMS2), variant-temperature NMR, pH, and solvent-dependent stability experiments have been performed (Figures S104−S115) The gMS2 results of P1− P3 by applying a graduated increase of the collision energy suggested a higher stability of P1 than that of P2 and P3 By
refluxing P1−P3 in 0.1 mol/L CH3COOH and 0.1 mol/L
Na2CO3,1H NMR spectra and ESI-MS data indicated that the Zn-based macromolecular architectures reported here were not acid and alkali resistant Besides, upon increasing the fraction
of CH3OH from 0% to 70% in the mixed solvents of CH3CN and CH3OH, there were no other pieces observed in ESI-MS data, proven the good solvent-dependent stability of P1, P2, and P3 Intermolecular interactions (such as electrostatic interactions) might affect the stability of the complexes.2b Transmission Electron Microscopy After confirming the formation of these three pinwheel-shaped architectures, we did our best to provide direct evidence for their configuration Unfortunately, even after multiple attempts, growing single crystals of P1−P3 that are suitable for X-ray analysis has failed
to date, and only powder-like solids have been obtained Transmission electron microscopy (TEM) experiments, which have been widely used to characterize microstructures, were alternatively performed to obtain structural insights.29Figure 6 shows the TEM images of pinwheel-shaped P1−P3 The averaged measured diameters of P1 (from 10 candidates), P2 (from 6 candidates), and P3 (from 7 candidates) were 6.8± 0.2, 9.2 ± 0.2, and 13.5 ± 0.1 nm, respectively, which were comparable to the molecular modeling diameters (6.7 nm for
Figure 5 Mass spectrometry for pinwheel-shaped hexagram P3: (A)
ESI-MS spectrum and (B) 2D ESI-TWIM-MS plot of P3.
Figure 6 Transmission electron microscopy for pinwheel-shaped P1-P3 TEM images of (A) P1, (B) P2, and (C) P1-P3.
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Trang 8P1, 9.6 nm for P2, and 13.6 nm for P3) More importantly, the
TEM images clearly showed each individual pinwheel-shaped
molecule with vertices and fan blades; P3 was observed as a
dispersion of hexagrams with a clear hollow structure
■ CONCLUSIONS
Pinwheels are fantastic memories of childhood; here, we
describe three nanometer-scale pinwheel-shaped metallo-supra
molecules, including a starlike trigon, a pentagram, and a
hexagram In the same way that DNA and proteins are made
up of specific sequences of nucleotides and amino acids,30
we prepared three intricate asymmetric metalloligands with
self-complementary features through delicate molecular designs by
first connecting three or more different individual organic
moieties with Ru2+ions These were then assembled with Zn2+
ions to form the pinwheel-shaped star trigon P1, pentagram
P2, and hexagram P3 in nearly quantitative yields In contrast
with most previously reported metallosupramolecules, this
formation is able to combine multiple components (up to
four) into one building block, which prevents the self-sorting
and restricts structuralflexibility To the best of our knowledge,
there is no previous report on metallo-organic ligands with
multiple different components (≥4) and multiple free
terpyridines (≥8) The successful manufacture of
pinwheel-shaped scaffolds of controlled shape provides a feasible and
effective strategy to construct increasingly complex molecular
topological structures Further investigations on the properties
of these giant supramolecules with special shapes are currently
underway
■ ASSOCIATED CONTENT
*s ı Supporting Information
The Supporting Information is available free of charge at
Experimental 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 Authors
Mingzhao Chen − 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 University, Guangzhou 510006, China;
Email:jinyulinzhao@foxmail.com
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 University, Guangzhou 510006, China;
csu.edu.cn
Authors
Jun 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
He Zhao − 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 Zhiyuan Jiang − 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
Feng 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 Guotao 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
Kaixiu Li − 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 Zhe Zhang − 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 University, Guangzhou 510006, China Die Liu − 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 University, Guangzhou 510006, China
Zhilong Jiang − 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 University, Guangzhou 510006, China Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.0c08020
Author Contributions
#J.W and H.Z contributed equally to this work
Notes
The authors declare no competingfinancial interest
We acknowledge support from the National Natural Science Foundation of China (21971257 to P.W and 22001047 to D.L.) and Guangdong Natural Science Foundation (2019A1515011358 to Z.Z.) The authors gratefully acknowl-edge the Center for Advanced Research in Central South University for the NMR measurements
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