Combining Synthesis and Self-Assembly in One Pot to Construct Complex 2D Metallo-Supramolecules Using Terpyridine and Pyrylium Salts

Article abstract of DOI:10.1021/jacs.9b05682

Multicomponent self-assembly in one pot provides an efficient way for constructing complex architectures using multiple types of building blocks with different levels of interactions orthogonally. The preparation of multiple types of building blocks typic

Full text of DOI:10.1021/jacs.9b05682

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Article
Combining Synthesis and Self-Assembly in One Pot to Construct Complex
2D Metallo-Supramolecules Using Terpyridine and Pyrylium Salts
Heng Wang, Yiming Li, Hao Yu, Bo Song, Shuai Lu, Xin-
Qi Hao, Yuan Zhang, Ming Wang, Saw-Wai Hla, and Xiaopeng Li
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 25 Jul 2019
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Combining Synthesis and Self-Assembly in One Pot to Construct
Complex 2D Metallo-Supramolecules Using Terpyridine and Pyrylium
Salts
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Heng Wang,† Yiming Li,† Hao Yu,‡ Bo Song,† Shuai Lu,†,§ Xin-Qi Hao,§ Yuan Zhang,∥ Ming Wang,‡
†
Saw-Wai Hla,∥ Xiaopeng Li*,
†Department of Chemistry, University of South Florida, Tampa, Florida 33620, United States
‡State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun,
Jilin 130012, China
§College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, Henan 450001, China
∥Nanoscience and Technology Division, Argonne National Laboratory, Lemont, Illinois 60439, USA
KEYWORDS pyrylium salts, terpyridine, supramolecular chemistry, multi-component self-assembly
ABSTRACT: Multi-component self-assembly in one-pot provides an efficient way for constructing complex architectures
using multiple-type of building blocks with different levels of interactions orthogonally. The preparation of multiple-type of
building blocks typically include tedious synthesis. Here, we developed a multi-component synthesis/self-assembly strategy,
which combined covalent interaction (C─N bond, formed through condensation of pyrylium salt with primary amine) and
metal-ligand interaction (N→Zn bond, formed through 2,2′:6′,2″-terpyridine-Zn coordination) in one pot. The high
compatibility of this pair of interactions smoothly and efficiently converted three and four types of components into desired
complex structures, i.e., supramolecular Kandinsky circles and spiderwebs, respectively.
Introduction
template driven synthesis of discrete supramolecules,22, 23
etc. These one-pot strategies rather than combining all
building blocks in a presynthesized ligand dramatically
reduced the barrier in ligand design and synthesis. However,
rational design of different levels of interactions in an
orthogonal manner to minimize unwanted products is still
full of challenges in the multi-component system and thus,
limits the complexity of metallo-supramolecules for further
advancement of functionality.
Nature, as
a talent programmer, codes extremely
sophisticated life information into proteins and DNAs
through combining multi-component in-situ reactions with
multi-level of non-covalent (hydrogen bonding, π-π, dipole-
dipole, etc.) and covalent (amidations or esterifications)
interactions in one biological system.1 Formation of discrete
assemblies from a pool of building block through “order-
out-of-chaos” approaches is emerging as one of the ultimate
goals of synthetic supramolecular chemistry in pursuing
higher level of complexity and desired functionalities.2
Among the diverse research fields of supramolecular
chemistry, coordination-driven self-assembly benefiting
from its highly directional and predictable feature has been
Beyond those boundaries, we herein developed a multi-
component synthesis/self-assembly strategy, which
enabled the construction of double layered supramolecular
Kandinsky Circles (KC) with three components, and
supramolecular spiderwebs with four components in one-
pot. Unlike subcomponent and template driven synthetic
strategies, such an attempt combined an irreversible
condensation of pyrylium salt and primary amine24
together with highly reversible 2,2′:6′,2″-terpyridine (tpy)-
Zn(II) coordination processes25 in one-pot without any
assistance from templates. This new approach not only
extensively applied to construct
a vast variety of
supramolecular architectures,3 including helicates,4 grids,5
rotaxanes,6 catenanes,7-9 links,10 knots,11 polygons,12-14 and
polyhedra.15-17 However, most of these studies focused on
building up metallo-supramolecules via a single type of
organic building block.
improved
the
synthetic
efficiency
of
desired
To achieve more sophisticated supramolecular systems
with higher efficiency, great efforts have been made on
multi-component self-assembly, such as social self-sorting
to compose a series of heteroleptic coordination sites,16e, 18-
supramolecules with increasing complexity, but also
enriched the library of the multi-component self-assembly.
20
subcomponent self-assembly based on reversible imine
17g, 21
bond formation and metal-ligand coordination,17f,
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one-pot synthesis/self-assembly. After deconvolution of
each peak, the measured molecular mass of the obtained
supramolecule was 17,413 Da in average, which exactly
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matches
the
molecular
composition
of
KC
3
[C846H732O18N78Zn12P30F180]. The experimental isotope
pattern of each charge state also agrees well with their
theoretical simulations based on the chemical composition
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of KC (Figure 1 insert, Figure S33). Traveling wave ion
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mobility-mass spectrometry (TWIM-MS)14k,
spectrum
presents a series of signals with narrow bands attributed to
KC species with successive charge state, indicating high
isomeric purity of the composed structure. NMR spectra
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including H, COSY and NOESY were collected (Figures S5-
11) and carefully compared with the results collected from
the supramolecule assembled via presynthesized ligand
strategy.14j No significant difference was observed between
the supramolecules prepared through these two strategies
(Figure S5), suggesting that the condensation and
coordination were compatible and orthogonal in such a
one-pot manner.
Scheme 1. Preparation of KC. (a) Conventional self-
assembly using presynthesized ligand L1; condition:
CHCl3/MeOH (1/3, v/v), 50 oC, 3 hours. (b) One-pot
approach with synthesis and self-assembly together using
precursors A and B; condition: DMSO, 110 oC, 24 hours. (c)
Synthesis of L1 from A and B, condition: DMSO, 120 C, 24
hours.
o
Results and Discussion
Self-assembly of double layered KC via one-pot
strategy. In our previous work, we assembled multi-
layered KCs using multi-topic tpy-pyridinium salts through
multi-step synthesis.14j, 14k Such KCs exhibited remarkable
antimicrobial activity against Gram-positive pathogen
methicillin-resistant Staphylococcus aureus (MRSA).
However, the tedious synthesis and challenging purification
of the charged multiarmed tpy-pyridinium ligands limited
the investigations of their properties and applications. As a
result, instead of using the conventional strategy (Scheme
1a), we tried to explore the possibility of directly
constructing KC through two precursors, i.e., pyrylium salt
A and primary amine B, with proper portion of Zn(II) in
one-pot (Scheme 1b). We hypothesized that the
condensation and the tpy-Zn coordination could be
orthogonal to facilitate this new type of in-situ
multicomponent synthesis/self-assembly. We speculated
the following three circumstances might occur: i) no
condensation happens, and a mixture of numerous mono-
layered circles is assembled by A/B with Zn(II)
narcissistically or socially; ii) condensation partially occurs,
and a mixture of ligand L1 and unreacted A/B form random
polymeric metallo-assemblies; iii) A and B are fully
converted, and the multi-component synthesis/assembly
perfectly generates a desired discrete structure.
Figure 1. (a) Full ESI-MS spectrum with theoretical and
experimental isotope patterns of 15+ species (right inset).
(b) TWIM-MS (m/z vs drift time) of KC composed by three-
component in-situ self-assembly strategy.
Precursors A/B and Zn(NO3)2 were mixed in DMSO with
the stoichiometric ratio (1/1/2). After 24 hours heating at
110 oC, the assembly was precipitated by adding excess
amount of NH4PF6 methanol solution, collected after simple
methanol wash, and directly subjected for characterization
without further purification. Electrospray ionization-mass
spectrometry (ESI-MS) was first utilized to address the
molecular composition of the obtained assembly. Mass
spectrum (Figure 1a) showed one dominant set of peaks
with continuous charge state from 11+ to 24+, suggesting a
discrete supramolecular structure was obtained during the
Carefully identifying the compositions among the
reaction mixture at each reaction stage offered us more
detailed information on understanding the mechanism of
the in-situ synthesis and self-assembly. ESI-MS was utilized
to monitor the assembly process, and results are shown in
Figure 2. At the earliest reaction stage (15 min after the
reaction mixture being heated at 110 oC, in order to dissolve
all reactants), an extremely messy spectrum was observed
with most peaks in the range of m/z 500~900, but no peak
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was detected for KC. Detailed analysis of these peaks
indicated that a mixture of B-Zn(II) macrocycles and A-B-
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Zn(II) macrocycles was formed at the very beginning of the
self-assembly (Figures S41a, b, Scheme S3a). Intriguingly,
A-B condensation intermediate, [A-B] (structure was
shown in Scheme S3b), was found to be assembled with
Zn(II) along with various amount of additional A and/or B
(Figures S41c, d, Scheme S3b-c). Such multiple entities were
regarded as the intermediate species prior to the formation
of our desired KC structure. After two hours of heating,
several peaks assigned to KC were observed and gradually
enhanced with increasing reaction time. Compared to the
rising of the sharp peaks of KC, all the other messy peaks
shrank and completely disappeared after 24 hours of
heating, indicating a complete conversion of A/B to form KC
(Figure 2).
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We gradually lowered the temperature from 110 oC to 50
oC to monitor the conversion process using ESI-MS, which
showed a significant increase of full conversion time
(Figures S42-44). The full conversion time for each reaction
temperature is 24 h at 110 oC, 60 h at 90 oC, 164 h at 70 oC,
and 456 h at 50 oC. Along with the conversion of the
intermediate species, clean sets of peaks of KC were
observed under all temperature conditions without other
impurities observed.
o
Figure 2. One-pot synthesis of KC at 110 C monitored via
ESI-MS at various reaction time.
Scheme 2. Preparation of (a) SW-1 and (b) SW-2 through four-component synthesis/self-assembly in one pot.
Condition: DMSO, 110 oC, 24 hours.
Self-assembly of Spiderweb-like supramolecules (SW-1
and SW-2) via one-pot strategy. To test the versatility of
this new one-pot strategy, we could design even more
complex supramolecules by simply changing organic
supramolecule can be constructed by replacing precursor B
with a tritopic tpy ligand C and adding hexatopic tpy ligand
D acting as a core in a four-component synthesis/self-
assembly (Scheme 2a). SW-1 was constructed by using the
same procedure of preparing KC. Only one dominant set of
precursors. For instance,
a
spiderweb-like (SW-1)
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sharp peaks is observed in the ESI-MS spectrum (Figure 3)
with various charge states (11+ to 24+). And the isotope
pattern of each charge state peak also agrees well with the
corresponding theoretical simulation result (Figure 3 insert
and Figure S34). The averaged molecular mass was
deconvoluted as 21,508 Da, which matches the chemical
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composition
(C996H678N114Zn18P42F252).
Furthermore,
TWIM-MS spectrum shows a series of narrowly distributed
signals, which indicates no isomers or conformers were
formed during the self-assembly. Collision cross sections
(CCSs),26b, 26c which are determined by the shape and size of
molecules, are derived through the drift time of SW-1
species with various charge state (results are summarized
in Table S2, Figure S48). The averaged measured CCSs is
2817.0 Å2, which is in good agreement with the calculated
CCSs result (2826.9 Å2) of SW-1. Note that the CCS of SW-1
is slightly larger than that of KC (2466 Å2).14j The excess CCS
value should come from the additional core structure of
SW-1 compared with KC. Further stability characterization
in gas phase was carried out by gradient tandem mass
spectrometry (gMS2)26 under various collision energies, as
shown in Figure S39. The 15+ ions of SW-1 totally
dissociated at 40 V, corresponding to a center-of-mass
collision energy at 0.08 eV. The dissociation voltage is much
higher than the corresponding total dissociation voltage of
15+ ions of KC (30 V, center-of-mass collision energy at 0.07
eV, Figure. S36), indicating a higher stability of SW-1 than
KC (in gas phase). Such enhanced stability is attributed to
the higher density of coordination sites (DOCS) of SW-1
(0.0064 site/Å2) than KC (0.0047 site/Å2).27
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Figure 3. (a) Full ESI-MS spectrum with theoretical and
experimental isotope patterns of 15+ species (right inset).
(b) TWIM-MS (m/z vs drift time) of SW-1 composed by four-
component in-situ self-assembly strategy.
Figure 4. 1H NMR spectra (600 MHz, d6-DMSO, 300 K) of (a) SW-1 and (b) SW-3.
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Apart from the one-pot strategy, another step-wise
as ca. 7.0 nm, which is consistent with the molecular
modeling result (Figure 6c). To obtain a higher resolution
image of SW-1, ultrahigh-vacuum, low-temperature
scanning tunneling microscopy (UHV-LT-STM) was utilized
to study the supramolecules on Ag(111) surface. As shown
in Figure 6a-b and Figure S51, high density of individual
SW-1 molecules are observed on the surface with hexagram
shape, and the diameter of each hexagram is also around 7.0
nm (Figure 6a). Note that, the bright dots in each hexagram
represent <tpy-Zn(II)-tpy> units due to their octahedral
coordination structure and higher electron density around
the metal ions. Two layers of bright lobes, i.e., a hexagonal
outer rim and a hexagonal inner ring, can be clearly
observed in Figure 6b. The larger lobes on the outer rim are
assigned to the two layers of <tpy-Zn(II)-tpy> units with
their signals merged together, while the smaller ones in the
inner ring are attributed to the <tpy-Zn(II)-tpy> junctions
linked to the hexatopic core (ligand D).
1
approach was also employed to construct SW-1. The step-
wise approach was illustrated in Scheme S2. Precursors C
and D were assembled with stoichiometric amount of Zn(II)
to produce a discrete supramolecular spokewheel (SW-3)28
with 6 reactive amino groups around the rim. ESI-MS of SW-
3 (Figure S36) displays one dominant set of sharp peaks
with continuous charges ranged from 8+ to 18+, as well as
well resolved isotope patterns (Figure S37). The
deconvoluted molar mass is 12,733 Da, matching its
chemical composition. Then, precursor A and additional
amount of Zn(II) were added into SW-3 solution. ESI-MS
showed that SW-1 was smoothly formed with the exactly
same ESI-MS spectrum as the one-pot method (Figure S45).
Such results further support the high orthogonality of the
tpy-Zn(II) coordination with the condensation reaction.
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Figure 4 shows the H NMR spectra of SW-1 and SW-3,
which provides more detailed structural information. In the
spectra of SW-3, three sets of peaks assigned to the protons
on the tpy groups can be figured out, corresponding to the
three different chemical environments of coordination sites
in the supramolecule, i.e., one on the outer rim edge, and
two on the spoke. Characteristic up field shifts of all a, b,
c6,6’’ are exhibited on the spectrum by comparing with the
metal free tpy contained ligands (Figure S1, 3, 4).14k, 28 In the
spectrum of SW-1 (Figure 4a), the characteristic peak of
amino protons of SW-3 shown around 5.4 ppm
disappeared; meanwhile, the new peak assigned to HJ of
pyridinium ring and the obvious down-field shift of HI
together prove the full conversion of amino group to
pyridinium group, during the formation of SW-1. Four sets
of tpy protonic peaks are exhibited in the spectrum,
corresponding to the additional layer of hexagonal ring by
comparing with SW-3. Again, the characteristic high field a-
d6,6’’ protonic signals are displayed, indicating the full
coordination of tpy groups with Zn(II) ions. In addition, all
peaks of SW-1 inner layer protons (HA-H, a,b,c-tpy-H) locate
in much high magnetic field area compared with the
corresponding signals of SW-3, which could be attributed to
the electron shielding effect from the hexagonal outer rim
on these inner ring protons. A 2D diffusion-ordered NMR
spectroscopy (2D-DOSY) analysis in d6-DMSO reveals a
single band at logD ≈ −10.5 (Figure S30), corresponding to
a discrete architecture. For comparison, the measured logD
value of SW-3 is ca. -10.3 (Figure S32), corresponding to its
much smaller diameter compared with SW-1. Using the
modified Stocks−Einstein equation based on the oblate
spheroid model (see Supporting Information for details),29
the experimental radii, i.e., the semimajor radius of SW-1
and SW-3 were calculated as 4.1 nm and 2.6 nm, which are
comparable with the results obtained from theoretical
models (3.9 nm shown in Figure 6c, and 2.8 nm shown in
Figure S54 ). The other NMR spectroscopic results are
summarized in the SI, including 2D COSY, 2D NOESY, 13C
NMR spectra (Figs. S12-29).
Figure 5. (a) Full ESI-MS spectrum with theoretical and
experimental isotope patterns of 15+ species (right inset).
(b) TWIM-MS (m/z vs drift time) of SW-2composed by four-
component in-situ self-assembly strategy.
In addition to the hexatopic tpy ligand D, two tritopic tpy
ligand E can act together as the cores to form another
discrete supramolecular spiderweb (SW-2) with four-
component synthesis/self-assembly in one pot, i.e.,
A/C/D/Zn, as shown in Scheme 2b.30 ESI-MS spectrum of
the resulted product (Figure 5) proves the structure with
desired chemical composition (C1002H684N114Zn18P42F252), by
displaying a series of sharp peaks with average measured
molecular mass as 21,585 Da. And the experimental
Transmission electron microscopy (TEM) was further
utilized to visualize individual supramolecules. Under TEM
imaging, a series of dots with narrowly dispersed diameters
was observed (Figure S50a). Zoomed-in image of one dot
shows a hexagon flake shape with the measured diameter
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Figure 6. (a) STM image of individual SW-1 on Ag(111) surface; (b) Zoomed-in STM image of one SW-1 supramolecule in (a),
(d) STM image of individual SW-2 on Ag(111) surface; (e) Zoomed-in STM image of one SW-2 supramolecule in (d); (c) and
(f) representative energy-minimized structures from molecular modeling of SW-1 and SW-2; alkyl chains were omitted for
clarity. Dash lines covered on the images of (b) and (e) represent the organic backbone of the complexes, pink ovals represent
the double-layers of <tpy-Zn(II)-tpy> junctions on the outer rim, and blue/green rounds correspond the <tpy-Zn(II)-tpy>
junction linked to the core.
the upper level of tritopic core (ligand E), while the lower
level of core cannot be detected by the tip.
isotope patterns of each charge states are consistent with
their corresponding theoretical ones (Figure 5 inset, and
Figure S35). TWIM-MS spectra of SW-2 also exhibits a
With such a new strategy in hand, we further explored the
narrowly distributed set of signal bands, corresponding to
selectivity of a more complicated system, i.e., selective
an averaged experimental CCS value as 2765.0 Å2, in good
assembly of SW-1 in the system containing precursors
agreement with the average theoretical CCS value as,
A/C/D/E and metal ions Zn(II) with the molar ratio
2761.8 Å2 (as shown in Table S2, Figure S49). The total
6/6/1/2/18, as illustrated in Scheme 3a. Instead of forming
dissociation voltage of SW-2 was measured with the same
a pool of mixtures, the five-component self-assembly
value as SW-1 in gMS2 spectra (40 V, Figure S40), owing to
precisely picked up A/C/D/Zn(II) with stoichiometric ratio
1
their similar DOCS values. The H NMR spectrum of SW-2
to form pure SW-1. ESI-MS spectrum of the obtained
shows similar signals as that of SW-1 (Figures S18-23) with
assembled product displays only one dominant set of sharp
four sets of tpy protonic resonance signals assigning to the
peaks, which exactly matches the chemical composition of
four different chemical environments of tpy-Zn(II)
SW-1 (Figure S46). Furthermore, complete core exchange
coordination sites. 2D-DOSY spectrum of SW-2 reveals a
was conducted by mixing equal amount of SW-2 and
single band of signals with the same logD value of SW-1 at
hexatopic ligand D at 110 oC (Scheme 3b). But such an
ca. −10.5 (Figure S31) with calculated radius as 4.1 nm
exchange procedure could not occur reversely by adding 2
(Figure 6f). TEM and STM images of SW-2 (Figure 6d-e,
eq. E into SW-1 solution. Increasing the amount of E could
Figure S50b, S52) also clearly shows hexagonal shaped
only partially convert SW-1 to SW-2 with unidentified
flakes of individual supramolecule with narrowly dispersed
assemblies as revealed by the messy ESI-MS spectrum
diameter at ca. 7.0 nm, further documenting the formation
(Figure S47). All these results suggest that SW-1 is a more
of desired structure. Zoomed-in STM image of SW-2 (Figure
energy favorable structure compared with SW-2. In this
6d) also shows the pattern with six larger signal lobes
five-component system, a self-recognition was realized in
arranged in the outer rim of a hexagon, and a triangular
the competition between D and E.
pattern in the inner ring. The observed inner patterns are
attributed to the three coordination junctions attached to
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Supporting Information. Synthetic details, molecular
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modeling, ligand and complex characterization, including H
NMR, 13C NMR, 2D COSY, 2D NOESY, 2D DOSY, ESI-MS, TWIM-
MS and additional TEM and STM images are included in
supporting information. This material is available free of
charge via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
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Corresponding Author
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* xiaopengli1@usf.edu
Notes
The authors declare no competing financial interest
ACKNOWLEDGMENT
This research was supported by the National Science
Foundation (CHE-1506722) and National Institutes of Health
(R01GM128037). Use of the Center for Nanoscale Materials, an
Office of Science user facility, was supported by the U.S.
Department of Energy, Office of Science, Office of Basic Energy
Sciences, under Contract No. DE-AC02-06CH11357. We also
acknowledge partial support by University of South Florida
Interdisciplinary NMR facility, and through a University of
South Florida Nexus Initiative (UNI) Award.
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(a) Bols, P. S.; Anderson, H. L., Template-Directed
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Scheme 1.Preparation of KC. (a) Conventional self-assembly using presynthesized ligand L1; condition:
CHCl /MeOH (1/3, v/v), 50 ℃, 3 hours. (b) One-pot ap-proach with synthesis and self-assembly together
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using precursors A and B; condition: DMSO, 110 ℃, 24 hours. (c) Synthesis of L1 from A and B, condition:
DMSO, 120 ℃, 24 hours.
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Figure 1. (a) Full ESI-MS spectrum with theoretical and experimental isotope patterns of 15+ species (right
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Figure 2. One-pot synthesis of KC at 110 ℃ monitored via ESI-MS at various reaction time.
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Scheme 2. Preparation of (a) SW-1 and (b) SW-2 through four-component synthesis/self-
assembly in one pot. Condition: DMSO, 110 ℃, 24 hours.
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Figure 3. (a) Full ESI-MS spectrum with theoretical and experimental isotope patterns of 15+ species (right
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Figure 4. H NMR spectra (600 MHz, d -DMSO, 300 K) of (a) SW-1 and (b) SW-3.
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Figure 5. (a) Full ESI-MS spectrum with theoretical and experimental isotope patterns of 15+ species (right
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Figure 6. (a) STM image of individual SW-1 on Ag(111) surface; (b) Zoomed-in STM image of one SW-1
supramolecule in (a), (d) STM image of individual SW-2 on Ag(111) surface; (e) Zoomed-in STM image of
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modeling of SW-1 and SW-2; alkyl chains were omitted for clarity. Dash lines covered on the images of (b)
and (e) represent the organic backbone of the complexes, pink ovals represent the double-layers of <tpy-
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linked to the core.
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Scheme 3. (a) Selective assembly of SW-1 through the synthesis/self-assembly in one pot strategy
involving two core ligands D and E. (b) Transforming SW-2 to SW-1 by adding equal equivalency of D.
Reaction condition: DMSO, 110 ℃, 24 hours.
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