Giant Truncated Metallo-Tetrahedron with Unexpected Supramolecular Aggregation Induced Emission Enhancement

Article abstract of DOI:10.1021/jacs.0c02366

The artificial synthesis of giant, three-dimensional, and shell-like architectures with growing complexity and novel functionalities is an especially challenging task for chemists. Fullerenes and self-assembled cages are remarkable examples that are proven milestones in the field of functional materials. Herein, we present another unique system: a giant terpyridine-based truncated metallo-tetrahedral architecture that includes densely-packed ionic pairs with a significant internal cavity. This huge metallo-tetrahedron with a molecular weight up to 70 000 Da was self-assembled simultaneously with 64 components: 12 large antler-shaped ligands (5), 4 star-shaped ligands (6), and 48 Cd²⁺ ions. Surprisingly, the giant tetrahedron shows broad visible emission (400-640 nm) and aggregation induced emission enhancement (AIEE) via a hierarchical assembly into highly-ordered nanoaggregates. A tunable emission color and near white-light emission in mixed solvent systems were also achieved. The present work not only affords an effective approach to the creation of giant shell-like architectures that can be used to mimic biological viruses and chemical frameworks but also provides a new class of functional metallo-architectures.

Full text of DOI:10.1021/jacs.0c02366

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Article
A Giant Truncated Metallo-tetrahedron with Unexpected
Supramolecular Aggregation Induced Emission Enhancement
Die Liu, Mingzhao Chen, Kaixiu Li, Zhengguang Li, Jian Huang, Jun Wang, Zhilong
Jiang, Zhe Zhang, Tingzheng Xie, George R. Newkome, and Pingshan Wang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c02366 • Publication Date (Web): 10 Apr 2020
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A Giant Truncated Metallo-tetrahedron with Unexpected
Supramolecular Aggregation Induced Emission Enhancement
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Die Liu,† Mingzhao Chen,† Kaixiu Li,‡ Zhengguang Li,‡ Jian Huang,‡ Jun Wang,‡ Zhilong Jiang,†
Zhe Zhang,† Tingzheng Xie,† George R. Newkome,¶ Pingshan Wang†,‡,*
†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
‡Hunan Key Laboratory of Micro & Nano Materials Interface Science; College of Chemistry and Chemical
Engineering, Central South University, Changsha, Hunan-410083, China
¶
Center for Molecular Biology and Biotechnology, Florida Atlantic University, 5353 Parkside Dr., Jupiter, FL-33458,
USA
Self-Assembly • Aggregation Induced Emission • Multitopic Terpyridine Ligands • Spoked Wheels
ABSTRACT: The artificial synthesis of giant, three-dimensional and shell-like architectures with growing complexity and
novel functionalities is an especially challenging task for chemists. Fullerenes and self-assembled cages are remarkable
examples that are proved milestones in the field of functional materials. Herein, we present another unique system: a giant
terpyridine-based truncated metallo-tetrahedral architecture that includes dense-packed ionic pairs with a significant
internal cavity. This huge metallo-tetrahedron with a molecular weight up to 70,000 Da was self-assembled simultaneously
with 64 components: 12 large antler-shaped ligands (5), 4 star-shaped ligands (6) and 48 Cd2+ ions. Surprisingly, the giant
tetrahedron shows broad visible emission (400-640 nm) and the aggregation induced emission enhancement (AIEE) via
hierarchical assembly into highly ordered nano-aggregates. Tunable emission color and near white-light emission in mixed
solvent systems were also achieved. The present work not only affords an effective approach to the creation of giant shell-
like architectures that can be used to mimic biological viruses and chemical frameworks but also provides a new class of
functional metallo-architectures.
example, Nitschke’s group synthesized a huge CoII12L6
INTRODUCTION
cuboctahedron, which was capable of cooperatively
binding anionic and neutral guests. Further, the bis-
fullerene receptor showed different cooperativity in
binding pairs of anions, which make it fit to construct the
programmable molecular systems. Fujita et al synthesized
the self-assembled PdII12L24 cage-like host with large size,
which was able to encapsulate the protein and such work
lay the foundation for regulating the conformation and
functionality of protein.43
Recently, the coordination-driven supramolecular cages
with aggregation-induced emission (AIE)44, 45 property and
their fascinating optical properties have drawn intense
attention.46-53 Among these architectures, the most were
generated by incorporating the tetraphenylethylene (TPE)
moieties to molecular scaffolds. For example, Stang and co-
Supramolecular polyhedral assemblies are quite
fascinating not only because of their aesthetically
appealing structures, but also due to their broad
applications ranging from catalysis,1, sensing,3-5 drug
2
delivery,6-8 separation and purify,9-12 to photophysical
applications.13 The most common and important kind of
these architectures were ones constructed by the
coordination-driven self-assembly, which possess the
highly directional and predictable feature to attain the
desirable structure with precise shapes and sizes. And a
great amount of excellent work, including tetrahedra,14-19
21
cubes,20, octahedra,22 cuboctahedra,23-25 dodecahedra,26
and others,2, 27-38 has been well demonstrated by Stoddart,
Stang, Fujita, Leigh, Nitschke, Newkome, and many others.
Several fascinating metallocages with various sizes,
shapes and functionality have been shown, but the giant,
complicated polyhedral structures assembled by more
than 60 components are uncommon due to the difficulty
associated with ligand design and assembly process.39-42
Despite these challenges, using chemical synthetic strategy
to create such multicomponent supramolecules to mimic
natural biological structures is still meaningful. For
workers
synthesized
the
pyridine-based
M12L24
nanospheres, which were covalently endo-anchored with
TPE moieties, displaying the stronger green light emission
in solution due to AIE effect on confined cavity.51 But the
cages without TPE moieties, yet possessing AIE effect, have
rarely been reported.50
2,2′:6′,2″-terpyridine (tpy) ligands could coordinate
with transition metal ions to generate linear <tpy-M-tpy>
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Scheme 1. Self-assembly and energy-minimized
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structures from molecular modeling of complex 7 (the
alkyl chains are omitted for clarity).
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Figure 1. Cartoon representation of vertical assembly of
double- and triple-decker hexagonal architectures and
polyhedral assembly of tetrahedron and octahedron from the
spoked wheel-like hexagon.
pseudooctahedral coordination connection and were ideal
candidates to construct 2D/3D self-assembled architect
55
ures.54, As shown in Scheme S1, the giant 2D shape-
persistent spoked wheel hexagons, firstly synthesized by
Newkome et al., were demonstrated to be incredibly
stable.56 So the hexagon is especially suitable as a plane
unit to construct complicated 3D structures. Surely, as
shown in Figure 1 and Scheme 1, by connecting the spoked
wheels with flexible alkyl linkers, the double- and triple-
decker hexagons were successfully synthesized via the
vertically extending the plane spoked wheels by our
group.57 But such strategy lead to the absence of cavities
for resultant assemblies and limited structural diversity. As
shown in Scheme 1, if using ligands with different, tailored
angles to install the directed rigid bridge to connect
hexagonal moieties, the cavities-containing polyhedrons,
including truncated tetrahedra, truncated octahedra and
truncated icosahedra, could be obtained in theory. In this
paper, we synthesized the dibenzo[b,d]furan bridged
ligands 5 containing two 2,8-position substitutional
tristerpyridines. Such ligands 5 (12 eq.) could assemble
with 6 (4 eq.) and Cd2+(48 eq.) to generate a giant cage-like
truncated tetrahedron, which consist of 64 components
and whose molecule weight up to 70 kDa. Unexpectedly,
this 3D supramolecular structure displayed the unusual
and appealing aggregation induced emission enhancement
(AIEE) effect.
As shown in Scheme 1, the self-assembly process began
by mixing 5 (3 eq.), 6 (1 eq.) and Cd(NO3)2·4H2O (12 eq.) in
CHCl3/MeOH at 65 ℃ for 24 h, yielding a translucent
colourless
solution.
Excess
lithium
bis(trifluoromethylsulfonyl)imide (LiNTf2) was then added
to give a precipitate, which was washed with MeOH and
H2O to generate (92%) complex 7, as a pale-yellow solid.
RESULTS AND DISCUSSION
As shown in Scheme 1 and Scheme S2, ligand 5 was
designed and synthesized by Suzuki coupling of the
bromo-substituted tristerpyridine monomer 4 with 2,8-
bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)
dibenzo[b,d]furan catalyzed by [Pd(PPh3)4]. Purification
was accomplished by column chromatography (Al2O3) and
1
subsequent recrystallization with CH2Cl2 and MeOH. H
NMR of 5 showed two set of peaks with 1:2 integrated ratio
attributed to two different terpyridinyl moieties, along
with a triplet at 3.12 ppm assigned to the methylene groups.
Structural characterization of 5 was further supported by
MALDI-TOF-MS analysis (Figure S13).
Figure 2. (a) 1H NMR spectra (500 MHz) of ligand 5 and 6 in
CDCl3 and complex 7 in CD3CN/[D7]DMF (4:1, v/v) and (b) 2D
DOSY NMR spectra of complex 7 (500 MHz, CD3CN/[D7]DMF
(4:1, v/v), 300 K).
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Figure 3. (a) ESI-MS and (b) 2D ESITWIM-MS plot (m/z vs
drift time) of complex 7. The charge states of intact assemblies
are marked.
Although the self-assembled complex 7 was a large
supramolecular architecture, its 1H NMR spectrum showed
a broad but yet distinguishable pattern. Firstly, when
comparing free ligand 5 and 6, the signals of tpyH3’,5’ and
tpyH3’,3’’ protons (Figure 2a) showed obvious downfield
shifts caused by the tangential electron-withdrawing
effects upon coordination. The tpyH6’,6’’ protons displayed
a dramatic up-field shift due to the electron shielding
effect.50 These signal changes demonstrated that the
assembled structure was generated. Furthermore, the
triplet at 3.12 ppm, assigned to methylene groups, split into
two peaks at 3.28 ppm and 3.32 ppm because of that the
free rotation of tris-terpyridine moieties was restricted and
the symmetry of 5 was broken, fully supporting the
formation of polyhedral structure. All of signals of protons
could been assigned by means of the 2D-COSY and NOESY
NMR.
Diffusion-ordered NMR spectroscopy (DOSY) spectrum
of tetrahedral complex 7 (Figure 2b) showed that the
protons signals of tetrahedral structure were on a narrow
band with log D = -9.96, supporting the formation of a
single discrete structure. The dynamic radius was
calculated by Stokes-Einstein equation to be 5.4 nm, which
was in accord with the energy-minimized tetrahedron
structure, verifying the formation of cage-like tetrahedron
structure. In addition, the signal corresponding to the
solvent DMF showed a series of continuous signals for
complex 7, indicating the cage-like complex 7 possessed a
large cavity and could encapsulate the DMF molecules in
order to restrict their free diffusion.
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Figure 4. (a) TEM image; (b) representative energy-
minimized structure, at top view; (c) AFM image and (d) a side
view of the energy-minimized structure of tetrahedral
structure 7.
match with the simulated m/z verifying the desired
truncated tetrahedral structure. Additional structural
evidence for complex 7 was provided by ESI-TWIM MS
experiments. The TWIM mass spectrum exhibited
continuous charge distributions ranging from 16+ to 30+
derived from 7, with a single band for every signal,
supporting the presence of a single species (Figure 3b).
Structural evidences were further obtained by the TEM
and AFM experiments. As depicted in Figures 4a and S18,
TEM images determined by drop casting of dilute
acetonitrile solutions of complex 7 (10−6~10−7M) onto
carbon film-coated Cu grid displayed the uniform particle
with an average diameter of 6.2 nm, which was in
accordance with the size of molecular modeling (6.5 nm,
Figure 4b). The AFM images (Figures 4c and S19)
obtained by dropping acetonitrile solutions (10−6~10−7M)
The ESI mass spectrum of 7 (Figure 3a) validated the
expected 64-component composition of [51264Cd48], in
which a series of peaks corresponding to sequential charge
states ranging from 16+ to 32+ were observed. The molecular
weight was 70759.78 Da, consistent with the molecular
−
formula of [Cd48(C2616H2040N288O60)]96+·96(NTf2 ). Although
the isotope pattern of each charge state in the mass
measurements was indistinct resulting from high
molecular weight and the giant cavity which encapsulated
the solvent molecules, this set of distinct signals presented
a
perfect
o n t o
f r e s h l y
c l e a v e d
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Figure 5. (a) UV/Vis absorption spectra, (b) fluorescence
Figure 6. TEM images of complex 7 in DMF (1%, v/v)/CH3CN
mixture with various CHCl3 fractions and corresponding
schematic illustration of aggregates: (a) schematic
representation of aggregates forming. (b) 30%. (c) 50%. (d)
70%. (e) 90%. (scale bar: 200 nm) And (f) DLS datum.
spectra (λex = 340 nm, c = 7 × 10−7 M), and (c) photographs (λex
= 365 nm, c = 7 × 10−7 M) of complex 7 in DMF (1%, v/v)/MeCN
mixture with adding various CHCl3 fractions.
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mica showed average height of 6.4 nm, which agreed with
the calculated height of model structure of 5.8 nm (Figure
4d).
Based on previous data, the tpy-based complexes
possessed excellent emission properties.58 The giant
tetrahedral 7, which possess 48 <tpy-Cd2+-tpy> moieties
(96 positive charges), was characterized by UV-Vis
absorption and
fluorescence experiments to evaluate its optical properties.
The UV-vis absorption spectrum in MeCN:DMF (7 × 10−7
M, 99:1, v/v) at 25 °C exhibited a distinct band with high
molar extinction coefficient at 285 nm assigned to ligand-
centered (LC) π-π* transitions and the band centered at
∼325 with the shoulder at ∼337 nm (Figure 5a), was
attributed to intraligand charge transfer (ILCT).59, 60 The
emission spectrum of complex 7 in a MeCN/DMF (99/1 in
v/v) solution showed two broad bands centered at 440 and
More fascinating, complex 7 exhibited aggregation
induced emission enhancement (AIEE), in which the
fluorescence intensity showed an obvious increment into
1.7, 3.2, 1.6, 1.1 and 4.6 times in the mixture with 95% poor
solvent corresponding to CH2Cl2, CHCl3, EtOAc, MeOH,
and H2O, respectively (Figure S31). The emission behavior
of complex 7 was further investigated in mixed systems
with different CHCl3 (or CH2Cl2) fractions. As shown in
Figures 5b, S31 and S33, the intensity of the band around ca.
500 nm was clearly enhanced and the band at ca. 440 nm
slightly enhanced by increasing the fraction of CHCl3 (or
CH2Cl2) from 10 to 90%. Accordingly, the emission color
changed from cyan to green for CHCl3 (Figure 5c) and to
yellow-green for CH2Cl2 (Figure S34) and the near white
light emission with coordination (0.2444, 0.3358) in the
Commission Internationale de L’Eclairage (CIE)
chromaticity diagram could be achieved (Figures S33 and
S35). In contrast, the emission intensity of ligand 5 and 6
showed a clear decrease due to aggregation, followed by
increasing the MeOH fraction from 10% to 90% in
CHCl3/MeOH mixture (Figure S30). The decreased
emission of 5 and 6 resulted from an aggregation-caused
quench (ACQ) effect, in which the π-π stacking of rigid π
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500 nm (Figure 5b), which could be presumably assigned
59, 60
to the π-π* and ILCT states
and almost covered the
entire visible spectral region (400−640nm).
conjugated 5 and 6 was easily formed via the compact
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aggregations (Figure S27).61,
However, π-π stacking
induced emission quench under aggregation is the
unfavorable result of the 3D configuration and ion pair
steric hindrance of this cage-like structure 7. We speculate
that the enhanced emission of complex 7 resulted from the
AIE behavior, in which the aggregation formed in a poor
solvent mixture (with higher CHCl3 concentration)
restricted intramolecular rotation (RIR) of the aromatic
rings.50, 63, 64 For the purpose of obtaining more evidence of
the aggregation, a series of UV-vis spectra were recorded
in a MeCN/CHCl3 system with the different fraction of
poor solvent e.g., CHCl3, from 10 to 90%. As shown in
Figures 5a and S28, the band at 285 nm decreased, with a
coincidental enhancement of absorbance at 370-400 nm,
demonstrating that complexes 7 were brought into close
proximity and formed aggregates.65
The sequentially aggregating in a poor solvent mixture
was schematically illustrated in Figure 6a. TEM and AFM
experiments afforded direct evidence for the formation of
aggregates. As displayed in Figures 6b-e and Figures S20-
26, the images determined by drop-casting the mixture
onto a Cu grid for TEM or mica sheet for AFM showed that
the
nanospherical
particles
formed
in
the
DMF/CH3CN/CHCl3 mixture. And the size of the
aggregates increased as the CHCl3 fraction increasing; the
average diameter of aggregates reached 185 nm from the
TEM images after adding 90% CHCl3. The size, determined
by TEM and AFM experiments, was obviously larger than
the results from DLS experiments, indicating that the
aggregates were unstable and easily collapsed to form
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Hydrogenation Independent of Remote Chain Length. J. Am.
Chem. Soc. 2019, 141, 11806-11810.
oblate structure on a solid surface. In order to obtain the
evidence for the aggregation behaviors, the dynamic light
scattering (DLS) experiments were performed in a mixed
DMF/MeCN/CHCl3 solvent. The results were shown in
Figure 6f, in which the average hydrodynamic diameters
(Dh) of 7 was determined to 5.6 nm in DMF/MeCN without
CHCl3, indicating no aggregation. However, the Dh
continuously changed from 12 to 147 nm with increasing
CHCl3 fractions from 10% to 90%, demonstrating that the
higher-order nano-aggregates were generated in the
DMF/MeCN/CHCl3 system.
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2.
Wei, J.; Zhao, L.; He, C.; Zheng, S.; Reek, J. N. H.; Duan,
C., Metal–Organic Capsules with NADH Mimics as Switchable
Selectivity Regulators for Photocatalytic Transfer Hydrogenation.
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Bravin, C.; Mason, G.; Licini, G.; Zonta, C., A
Diastereodynamic Probe Transducing Molecular Length into
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Bravin, C.; Guidetti, A.; Licini, G.; Zonta, C.,
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Jiang, X.-F.; Hau, F. K.-W.; Sun, Q.-F.; Yu, S.-Y.; Yam, V.
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W.-W., From {AuI···AuI}-Coupled Cages to the Cage-Built 2-D
{AuI···AuI} Arrays: AuI···AuI Bonding Interaction Driven Self-
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In conclusion, the giant truncated tetrahedron 7 with the
molecular weight up to 70,000 Da was nearly qualitatively
synthesized via a one-pot self-assembly of 64 components.
The composition and structure were characterized by a
6.
Lewis, J. E. M.; Gavey, E. L.; Cameron, S. A.; Crowley, J.
1
D., Stimuli-responsive Pd2L4 metallosupramolecular cages:
towards targeted cisplatin drug delivery. Chem. Sci. 2012, 3, 778-
784.
combination of H NMR, DOSY NMR, DLS, ESI-MS,
TWIM-MS, TEM and AFM images. More importantly, the
multicharged metal-organic complex 7 was able to further
self-assemble into highly ordered nano-aggregates and
showed that the aggregation-induced emission
enhancement, along with tunable emission color and near
white-light emission in mixed solvent systems. This
research provides new insight into optically-active
metallo-supramolecules obtained by a simple, one-step
rational design.
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Schmidt, A.; Casini, A.; Kühn, F. E., Self-assembled M2L4
coordination cages: Synthesis and potential applications. Coord.
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ASSOCIATED CONTENT
The Supporting Information is available free of charge on the
ACS Publications website at http://pubs.acs.org at DOI:
10.1021/. Experimental procedures and characterization data,
including 1H, 13C, COSY, NOESY, and DOSY spectra of the new
compounds and ESI-MS spectra, TEM and AFM images of
related compounds (PDF)
10.
Liu, J.; Duan, W.; Song, J.; Guo, X.; Wang, Z.; Shi, X.;
Liang, J.; Wang, J.; Cheng, P.; Chen, Y.; Zaworotko, M. J.; Zhang,
Z., Self-Healing Hyper-Cross-Linked Metal–Organic Polyhedra
(HCMOPs) Membranes with Antimicrobial Activity and Highly
Selective Separation Properties. J. Am. Chem. Soc. 2019, 141, 12064-
12070.
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Zhang, H.-N.; Lu, Y.; Gao, W.-X.; Lin, Y.-J.; Jin, G.-X.,
AUTHOR INFORMATION
Selective Encapsulation and Separation of Dihalobenzene Isomers
with Discrete Heterometallic Macrocages. Chem. - Eur. J. 2018, 24,
18913-18921.
Corresponding Author
*P. Wang: chemwps@csu.edu.cn.
12.
Kieffer, M.; Garcia, A. M.; Haynes, C. J. E.; Kralj, S.;
ORCID
Iglesias, D.; Nitschke, J. R.; Marchesan, S., Embedding and
Positioning of Two FeII4L4 Cages in Supramolecular Tripeptide
Gels for Selective Chemical Segregation. Angew. Chem. Int. Ed.
2019, 58, 7982-7986.
Pingshan Wang: 0000-0002-1988-7604.
Die Liu: 0000-0002-3918-0569.
13.
Saha, M. L.; Yan, X.; Stang, P. J., Photophysical
Notes
Properties of Organoplatinum(II) Compounds and Derived Self-
Assembled Metallacycles and Metallacages: Fluorescence and its
Applications. Acc. Chem. Res. 2016, 49, 2527-2539.
The authors declare no competing financial interest.
ACKNOWLEDGMENT
14.
Kaphan, D. M.; Levin, M. D.; Bergman, R. G.; Raymond,
This research was supported by the National Natural Science
Foundation of China (21971257) and the Hunan Provincial
Science and Technology Plan Project of China (No.
2019TP1001) for P.W., the Natural Science Foundation of
Guangdong Province, China (No. 2019A1515011358) for Z. Z..
The authors grateful acknowledge Prof. Dr. Carol D. Kercher
for her professional consultation.
K. N.; Toste, F. D., A supramolecular microenvironment strategy
for transition metal catalysis. Science 2015, 350, 1235-1238.
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molecular assembly held together by 60 hydrogen bonds. Nature
1997, 389, 469-472.
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MacGillivray, L. R.; Atwood, J. L., A chiral spherical
Roberts, D. A.; Pilgrim, B. S.; Cooper, J. D.; Ronson, T.
K.; Zarra, S.; Nitschke, J. R., Post-assembly Modification of
Tetrazine-Edged FeII L6 Tetrahedra. J. Am. Chem. Soc. 2015, 137,
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A Giant Truncated Metallo-tetrahedron with Unexpected Supramolecular Aggregation Induced Emission
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