Multicomponent Metallo-Supramolecular Nanocapsules Assembled from Calix[4]resorcinarene-Based Terpyridine Ligands

Article abstract of DOI:10.1021/jacs.0c01482

Tetrafunctionalized calix[4]resorcinarene cavitands commonly serve as supramolecular scaffolds for construction of coordination-driven self-assembled capsules. However, due to the calix-like shape, the structural diversity of assemblies is mostly restrict

Full text of DOI:10.1021/jacs.0c01482

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Article
Multicomponent Metallo-Supramolecular Nanocapsules
Assembled from Calix[4]resorcinarene-Based Terpyridine Ligands
Lipeng He, Shi-Cheng Wang, Lin-Ting Lin, Jhen-Yu Cai, Lijie Li, Tsung-Han Tu, and Yi-Tsu Chan
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c01482 • Publication Date (Web): 09 Mar 2020
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Multicomponent Metallo-Supramolecular Nanocapsules Assembled
from Calix[4]resorcinarene-Based Terpyridine Ligands
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Lipeng He, Shi-Cheng Wang, Lin-Ting Lin, Jhen-Yu Cai, Lijie Li, Tsung-Han Tu, and Yi-Tsu
Chan*
Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei, 10617, Taiwan
ABSTRACT: Tetrafunctionalized calix[4]resorcinarene cavitands commonly serve as supramolecular scaffolds for construc-
tion of coordination-driven self-assembled capsules. However, due to the calix-like shape, the structural diversity of assem-
blies is mostly restricted to dimeric and hexameric capsules. Previously, we reported a spontaneous heteroleptic complex-
ation strategy based on a pair of self-recognizable terpyridine-based ligands and CdII ions. Building on this complementary
ligand pairing system, herein three types of nanocapsules, including a dimeric capsule, a Sierpiński triangular prism, and a
cubic star, could be readily obtained through dynamic complexation reactions between a tetratopic cavitand-based ligand
and various multitopic counterparts in the presence of CdII ions. The dimeric capsular assemblies display the spacer-length-
dependent self-sorting behavior in a four-component system. Moreover, the precise multicomponent self-assembly of a
Sierpiński triangular prism and a cubic star possessing three and six cavitand-based motifs, respectively, demonstrates that
such self-assembly methodology is able to efficiently enhance architectural complexity for calix[4]resorcinarene-containing
metallo-supramolecules.
metallo-supramolecules through multicomponent self-as-
INTRODUCTION
sembly, producing various outputs such as prisms,36-41 tre-
foil knots,42-43 molecular muscles,44-48 shuttles,49-52 and cat-
alytic machinery.53-56 Among them, 2,2':6',2"-terpyridine
(tpy) ligands have recently attracted considerable atten-
tion because of their adjustable coordination lability and
excellent solubility to maintain homogeneity in self-assem-
bly.57-58 Due to the pseudo-octahedral coordination geom-
etry of <tpy‒MII‒tpy>, organic molecules, such as carba-
zole,59 porphyrin,60 adamantane,61-62 and crown ethers,63-65
are commonly selected as a core to create proper geometric
angles. Robust <tpy‒RuII‒tpy> derivatives are often func-
tionalized to afford a variety of metalloligands in a stepwise
manner, so as to suppress formation of mismatched assem-
blies.66-76 To lessen the synthetic burden, we have demon-
strated that the tpy ligand modified by 2,6-dimethoxy-
phenyl substituents at 6,6"-tpy positions can spontane-
ously form a heteroleptic complex with an unsubstituted
tpy ligand in the presence of CdII ions.33 Given this molec-
ular self-recognition, the quantitative self-assembly of a
number of 2D and 3D metallo-supramolecular architec-
tures has been successfully realized.77-78 To further explore
self-assembly behavior of the fourfold symmetric cavitand-
based tpy ligand with complementary counterparts, herein
we focus our investigations on the construction of multi-
component nanocapsules bearing calix[4]resorcinarenes.
Inspired by the ability of enzymes to encapsulate sub-
strates and convert them into products,1 construction of
molecular containers or capsules has been an attractive re-
search field for a few decades. One of the most successful
examples is the hexameric calix[4]resorcinarene capsule
originally disclosed by Atwood.2 Since the seminal discov-
ery, resorcinarene-based building blocks with fourfold
symmetry have been widely utilized in construction of su-
pramolecular capsules via either dynamic covalent bonds3-
4
or noncovalent interactions.5-13 and their applications in
host-guest chemistry14-19 and catalysis20-24 have been ex-
ploited as well. In coordination-driven self-assembly, the
calix-shaped scaffold could readily facilitate the formation
of dimeric and hexameric capsules,5-9,12 but the challenge
remains to further enhance the topological diversity and
complexity of resorcinarene-based capsular assemblies. To
this end, introduction of shape-complementary connect-
ors might lead to various nanocapsules with tunable cavity
size and geometry, and therefore dynamic heteroleptic co-
ordination with high fidelity becomes a pivotal tool for pre-
cisely connecting preprogrammed molecular subunits.
In the field of supramolecular coordination chemistry,
dynamic heteroleptic mononuclear metal complexes have
been achieved through delicate molecular designs, e.g.,
preference of coordination geometry.25-27 steric hin-
drance,28-34 and electrostatic interactions.35 Indeed, the
self-selective coordination approaches provided facile ac-
cess to construction of discrete well-defined heteroleptic
As shown in Scheme 1, three kinds of metallo-supramo-
lecular assemblies, namely a dimeric capsule, a Sierpiński
triangular prism, and a cubic star, were constructed in
quantitative yields through single-step heteroleptic cad-
mium(II) complexation of the calix[4]resorcinarene-based
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tpy ligand (L1) with di-, tetra-, and tri-topic ligands, respec-
Scheme 1. Calix[4]resorcinarene-Based Nanocapsules
Assembled via Dynamic Heteroleptic Terpyridine
Complexation
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tively. The self-sorting behavior of dimeric capsules was ex-
amined using three-ligand systems. The result indicated
that a slight difference in spacer length between the ditopic
ligands markedly varied the populations of the resultant
capsules. The novel molecular prism with two Sierpiński
triangles stacked in a face-to-face orientation was achieved
by the combination of two complementary tetratopic lig-
ands. Eventually, the giant cubic star bearing six calix[4]re-
sorcinarene subunits with a molecular weight of 37,192 Da
was realized, and its well-defined geometry was evident
from the sharp 1H NMR resonances and the TEM images.
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Figure 1. (a) Molecular structures and cartoon representations of the ligands L1-L4 and corresponding dimeric capsules. (b) 1H and
(c) 113Cd NMR spectra of dimeric capsules [Cd8L12L2 ], [Cd8L12L3 ], and [Cd8L12L4 ].
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coupling reaction of the tetrabrominated methylene-
bridged calix[4]resorcinarene with 6,6"-disubstituted-ter-
pyridylphenylboronic acid pinacol ester (Scheme S1). To
construct dimeric capsules, we aim to synthesize a series of
unsubstituted bis-tpy ligands with appropriate bend angles
RESULTS AND DISCUSSION
Self-Assembly of Dimeric Capsules [Cd8L12L2 ],
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[Cd8L12L3 ], and [Cd8L12L4 ]. The calix[4]resorcinarene-
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based tpy ligand L1 was synthesized by the Suzuki-Miyaura
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and directionality. Considering the conical angle of 64° de-
[Cd8L12L2 ], [Cd8L12L3 ], and [Cd8L12L4 ], respectively, indi-
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rived from L1 (Scheme 1),3,12 120o-bent bis-tpy ligands are
applicable to formation of two crossed rhombi in a capsule.
Hence, three ligands with varying spacer lengths, L2, L3 and
L4, were designed and synthesized (Figure 1a). L2 was pre-
pared according to the reported protocol (Schemes S2).67
L3 and L4 were synthesized through the Suzuki-Miyaura
coupling reactions of 4-t-butyl-2,6-diiodoanisole with the
corresponding terpyridylphenylboronic acids (Schemes S3
and S4). To fulfill maximum site occupancy, L1 and com-
plementary ligands L2-L4 were respectively mixed with
Cd(NO3)2 in a 1:2:4 molar ratio in CHCl3/MeOH/MeCN
(1:1:1, v/v/v), all of which led to homogeneous solutions. Af-
cating the formation of a single assembly in each case. Fur-
thermore, the 113Cd NMR spectra of these symmetric cap-
sules revealed sharp singlets (Figure 1c), implying that the
CdII centers of each capsule reside in the same chemical
environment as expected.
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ESI-MS and TWIM-MS measurements provided conclu-
sive evidence for the composition and structures of these
assemblies (Figures 2, S27, S37, and S47). As shown in Fig-
ure 2, the ESI-MS spectra of the abovementioned com-
plexes showed clean, distinct peak distributions. For exam-
ple, a set of peaks attributed to 4+ to 12+ charge states was
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observed and assigned as the desired capsule [Cd8L12L2 ]
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−
o
ter the solutions were stirred at 60 C for 12 h, an excess
losing the corresponding number of counterions (PF6 ).
Moreover, the experimental isotope patterns of [Cd8L12L2 ]
amount of NH4PF6 in MeOH was added to afford the coun-
terion-exchanged complexes, which were subsequently
dissolved in CD3CN and heated at 80 °C. 1H NMR and ESI-
MS were employed to monitor the self-assembly process.
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were in good agreement with the theoretical ones (Figure
S28). Similarly, the ESI-MS analyses (Figures 2b and 2c)
also strongly supported the formation of [Cd8L12L3 ] and
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[Cd8L12L4 ]. Our attempts to grow single crystals for X-ray
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crystallographic analysis were unsuccessful. Alternatively,
TWIM-MS was utilized to provide additional structural in-
formation.67,79-82 By comparing the experimental collision
cross-sections (CCSs) derived from TWIM-MS with the
theoretical ones calculated by the projection approxima-
tion (PA) and the trajectory method (TM) using
MOBCAL,83-84 the proposed structures can be further veri-
fied. For instance, the TWIM-MS plot of [Cd8L12L2 ] (Figure
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S27b) revealed narrow drift time distributions (DTDs) for
the 5+ to 12+ ions, indicating the quantitative formation of
a sole construct. Moreover, the average experimental CCS
of 1138.7 ± 41.7 Å2 was in good accord with the theoretical
values generated from 200 energy-minimized candidates
of the proposed dimeric capsule (Table S1). In the case of
[Cd8L12L3 ], narrow DTDs were observed as well (Figure
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S37b), and the experimental CCS (1313.6 ± 67.8 Å2) agreed
well with the theoretical ones. Notably, the TWIM-MS plot
of the largest capsule [Cd8L12L4 ] with a rim-to-rim distance
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of 5.1 nm in this series exhibited two stair patterns and two
explicit DTDs for the 10+ ions (Figure S47b), presumably
due to the balance between the flexible conformation and
the repulsive Coulombic force.85-87 This observation also
confirmed that [Cd8L12L4 ] has higher conformational flex-
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ibility stemming from the longer spacer length of L4 (Fig-
ure 1a).
Figure 2. ESI-MS spectra and isotope patterns of dimeric cap-
sules (a) [Cd8L12L2 ], (b) [Cd8L12L3 ], and (c) [Cd8L12L4 ].
Self-Sorting Experiments. The self-sorting behavior of
the three-ligand system containing L1 with two kinds of
120°-bent bis-tpy ligands was investigated. It was found
that an equimolar mixture of L1, L2, and L4 in the presence
of 4 equiv of CdII ions gave narcissistically self-sorted
[Cd8L12L2 ] and [Cd8L12L4 ], which were confirmed by NMR,
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After 8-hour heating, the 1H NMR signals of the resultant
complexes were sharp and well-resolved (Figure 1b). The
COSY and ROESY experiments (Figures S21-24, S31-S34 and
S41-44) further confirmed the proper assignments. Notably,
the outward (α) and inward (α') resonances for the meth-
ylene bridges of L1 were shifted downfield as compared
with uncoordinated L1. In addition, the 3',5'-tpy protons of
L2-L4 had significant upfield shifts due to the electron
shielding effect caused by the heteroleptic complexation.33
The DOSY experiments (Figures S25, S35 and S45) revealed
one set of signals with identical diffusion coefficients (D)
of 6.46 × 10-10, 4.90 × 10-10, and 4.37 × 10-10 m2s−1 for
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ESI-MS and TWIM-MS (Figure 3). The H and 113Cd NMR
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spectra (Figures 3b and 3c) revealed two distinguishable
sets of peaks corresponding to the capsules [Cd8L12L2 ] and
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[Cd8L12L4 ], respectively. ESI-MS (Figure 3d) and TWIM-
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MS (Figure 3e) further verified the self-sorted result. In
contrast, dynamic combinatorial libraries of [Cd8L12L2 L3
n
4-
n] and [Cd8L12L3 L44-n] (n = o-4) were generated upon the
n
complexation of L1/L2/L3 or L1/L3/L4 with CdII ions in the
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same molar ratio (Schemes S10 and S12). The 1H NMR spec-
showed the peaks arising from all five possible composi-
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tra of the resulting mixtures (Figures S50 and S54) showed
sharp peaks, but the large number of overlapping 1H NMR
signals hampered the proper assignments for each compo-
nent. Instead, ESI-MS analyses (Figures S51 and S55) clearly
tions. Building on the above observations, the spacer
length difference indeed played a pivotal role in the self-
sorting process. Only when the difference reached a bi-
phenyl unit long, the combinatorial library of six capsules
could be self-sorted into two well-defined species.
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Figure 3. (a) Cartoon representation of the self-sorting event. (b) H and (c) 113Cd NMR spectra of [Cd8L12L2 ], the self-sorted
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mixture, and [Cd8L12L4 ]. (d) ESI-MS and (e) TWIM-MS spectra of the self-sorted [Cd8L12L2 ] and [Cd8L12L4 ].
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Self-Assembly of Sierpiński Triangular Prism
CHCl3/MeOH/MeCN (1:1:1, v/v/v). After the counterion ex-
change with excess NH4PF6, a white solid was obtained in
quantitative yield. The product was then dissolved in
CD3CN and heated at 80 oC for 9 days. Eventually, the for-
[Cd18L13L5 ]. The Sierpiński triangles are a set of mathemat-
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ically generated patterns with self-similarity named after
Waclaw Sierpiński.88 In the past decades, this well-known
geometry has attracted tremendous interests in various
fields of science. Chemists have constructed Sierpiński tri-
angles successfully via supramolecular self-assembly using
hydrogen bonding,89 synergistic halogen and hydrogen
bonding,90 metal-ligand coordination,77,91-98 and dynamic
covalent bond.99-100 However, these studies are focused
more on the preparation of different generations of 2D
Sierpiński triangles, and less on the 3D analogues. Here, we
demonstrate the facile construction of a novel Sierpiński
triangular prism through the heteroleptic complexation of
L1 with tetrakis-tpy ligand L5 (Figure 4a).
mation of [Cd18L13L5 ] was confirmed by NMR and ESI-MS.
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The H NMR spectra (Figure 4b) showed that the charac-
teristic singlet for 3',5'-tpy protons of L1 was shifted down-
field from 8.6 to 9.1 ppm after complexation. Moreover,
two singlets at δ 8.4 and 8.7 ppm for 3',5'-tpy protons of L5
were partially overlapped with other signals, but still could
be identified as the heteroleptic and homoleptic moieties,
respectively, by the COSY and ROESY experiments (Fig-
ures S57-S60). It is worth noting that the signals for a, α, α',
and β protons of the calix[4]resorcinarene core were split
into two sets with identical intensities, which agreed well
with the fact that the calix[4]resorcinarene moiety in L1 has
two different chemical environments after formation of the
proposed prismatic structure. In addition, the signals for d
and f protons of ligand L1 were also split into two sets with
equal intensities. The 1H−1H exchange spectroscopy (EXSY)
experiment (Figure S61) suggested that the unusual peak
splitting originated from a slow exchange of the corre-
sponding protons,101-102 possibly due to the ion-dipole inter-
actions between the CdII center and methoxy units. The
Since <tpy‒MII‒tpy> connectivity generally serves as
edges in metallo-supramolecular architectures, a combina-
tion of 60o-bent bis-tpy and K-shaped tetrakis-tpy ligands
is essential for the construction of a first-generation Sier-
piński triangle.77,91 Therefore, we anticipated that ligand L1
might function as a clip to afford a triangular prism. To test
our hypothesis, the mixture of L1, L5, and Cd(NO3)2 in a mo-
lar ratio of 1:2:6 was heated at 60 oC for 2 days in
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5a) and the corresponding isotope patterns (Figure S64).
DOSY spectrum (Figure S62) exhibited a single assembly
with a diffusion coefficient of 3.63 × 10-10 m2s−1, and the 113Cd
NMR spectrum (Figure S63) showed two singlets at δ
270.08 and 243.30 ppm with an integration ratio of 1:2,
which were assigned to the homoleptic and heteroleptic
CdII centers, respectively. Eventually, the chemical formula
The narrow DTDs in the TWIM-MS plot (Figure 5b) ex-
cluded the presence of isomeric structures. Although the
inflated conformations were observed for the 15+ to 17+
ions due to the increased Coulombic repulsion, the average
experimental CCS of 2082.1 ± 64.5 Å2 was still consistent
with the theoretical ones (Table S4).
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of [Cd18L13L5 ] was unambiguously determined by the ma-
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jor ESI-MS signals derived from the 8+ to 18+ ions (Figure
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Figure 4. (a) Molecular structures and cartoon representations of the ligands L1 and L5 and Sierpiński triangular prism, and (b) 1H
NMR spectra of L1, L5 and [Cd18L13L5 ].
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Self-Assembly of Cubic Star [Cd24L16L6 ]. Aiming for
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construction of other cavitand-based self-assemblies with
high structural complexity, a stellated capsule possessing
six resorcinarenes was designed (Figure 6). In geometry,
stellated polyhedrons can be created by extending the fa-
cial planes of a polyhedron until the new closed boundaries
are formed.103 According to Miller’s rules,104 stellation of a
cube cannot be realized because its parallel non-adjacent
faces cannot be extended to meet in a new boundary. How-
ever, a star-shaped cube can be established by augmenta-
tion,105 which is the process of replacing the faces of a cube
with square pyramids of identical height (h) (Figure 6a).
When the height of pyramids reaches 50% of the edge
length (l) of a cube (h/l = 0.5), a rhombic dodecahedron
consisting of 12 rhombic faces, 24 edges, and 14 vertices of
two types is generated. In our molecular design, we ex-
pected that the tetratopic ligand L1 would serve as the ver-
Figure 5. (a) ESI-MS and (b) TWIM-MS spectra of [Cd18L13L5 ].
tex of a square pyramid when assembled with the trigonal
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connector L6 to produce a stellated capsule (Figure 6b). rhombic dodecahedron,106 we defined the capsular assem-
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The energy-minimized model of the assembly (Figure S72
and Video S1) displayed that the h/l value is approaching
1.1 (Figure 73). Therefore, instead of using the name of
bly as a cubic star, which has 12 puckered rhombi as the
faces (Figure S73).
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Figure 6. (a) Augmentation of a cube to generate a rhombic dodecahedron and a cubic star. (b) Molecular structures and cartoon
representations of the ligands L1 and L6 and self-assembled cubic star, (c) 1H NMR spectra of L1, [Cd24L16L6 ], and L6 and (d) 113Cd
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NMR spectrum of [Cd24L16L6 ].
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To achieve the single-step self-assembly of the proposed
gain more structural insights into individual Sierpiński tri-
angular prism [Cd18L13L5 ] and cubic star [Cd24L16L6 ]. The
cubic star, the mixture of L1 (3 equiv), tris-tpy ligand L6 (4
equiv), and Cd(NO3)2 (12 equiv) was heated in
CHCl3/MeOH/MeCN (1:1:1, v/v/v) at 60 °C for 2 days. The
solution was treated with excess NH4PF6 to give a pale yel-
low precipitate with PF6− as counterions, which was re-dis-
solved in CD3CN and then heated at 80 °C for 2 days. The
1H NMR spectrum (Figure 6c) showed a set of very sharp
and well-resolved peaks, implying that the high purity and
well-defined geometry of the resultant complex. The full
assignments were further confirmed by the COSY and
ROESY experiments (Figures S67-S69). A single diffusion
coefficient of 2.63 × 10-10 m2s−1 for the related peaks in
CD3CN measured by DOSY (Figure S70) and a sharp 113Cd
NMR singlet at δ 241.61 ppm (Figure 6d) strongly suggested
the formation of a highly symmetric assembly after com-
plexation. Furthermore, the assembled composition was
verified by ESI-MS (Figure 7a), which displayed one series
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TEM image of [Cd18L13L5 ] (Figure 8a) displayed a number
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of features having similar dimensions, and the average di-
ameter was estimated to be 4.5 ± 0.4 nm by circle fitting,
which agreed well with the modeled rim-to-rim distance
(4.9 nm). Notably, the triangular patterns could be found
in higher magnification (Figure 8b). In the case of
[Cd24L16L6 ], besides some aggregated particles, the TEM
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micrographs revealed hexapod-shaped particles with an
average diameter of 5.6 ± 0.5 nm (Figures 8c, 8d and S74a),
which is in the size range between the simulated adjacent
(4.6 nm) and opposite (6.3 nm) rim-to-rim distances. The
average heights measured by AFM were 4.0 ± 0.6 and 5.9 ±
1.0 nm for [Cd18L13L5 ] and [Cd24L16L6 ], respectively, and
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consistent with the corresponding theoretical dimensions
(Figure S75).
of dominant peaks corresponding to the ions of [Cd24L16L6 ]
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at the charge states ranging from 11+ to 30+. Possibly owing
to the high molecular weight (37,192 Da), multiple coun-
terions, and the resolution limitation of the mass spec-
trometer, the well-resolved isotope patterns for each major
peak could not be obtained. Additionally, a minor peak dis-
tribution with larger m/z ratios was observed and assigned
to the formula of [Cd24L16L6 ] plus one MeOH and two
8
NH4PF6 (see the Supporting Information). Again, the high
conformational flexibility of [Cd24L16L6 ] was reflected by
8
three stair patterns in the TWIM-MS plot (Figure 7b), in-
cluding the DTDs at charge states from 15+ to 19+, from 19+
to 22+, and from 21+ to 27+.85-87 Because of the charge-in-
duced conformational change, the corresponding CCS val-
ues were increased significantly with increasing number of
positive charges, and gave rise to the average experimental
CCS of 3141.5 ± 206.4 Å2 with a larger standard deviation
(Table S5).
Figure 8. TEM images of (a,b) [Cd18L13L5 ] and (c,d)
6
[Cd24L16L6 ].
8
CONCLUSIONS
The single-step quantitative self-assembly of a series of
cavitand-based metallo-supramolecules, including three
dimeric capsules, a Sierpiński triangular prism, and a cubic
star, has been achieved via heteroleptic complexation of
CdII cations with the calix[4]resorcinarene-based tpy lig-
and and complementary bis-, tetrakis-, and tris-tpy ligands.
The spontaneous heteroleptic complexation indeed en-
hanced topological diversity and complexity of the ca-
lix[4]resorcinarene-based nanocapsules. It was found that
the cavity size of the dimeric capsules could be readily
modulated by the bis-tpy ligands of varying spacer length,
and their self-sorting behavior in a three-ligand system was
proven to be spacer-length dependent. Besides, the un-
precedented Sierpiński triangular prism was successfully
established, and the study will allow us to further develop
the precise self-assembly of elaborate 3D fractal structures
such as a Sierpiński tetrahedron. Finally, the giant cubic
Figure 7. (a) ESI-MS and (b) TWIM-MS spectra of
[Cd24L16L6 ].
8
Transmission electron microscopy (TEM) and atomic
force microscopy (AFM) experiments were conducted to
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 8 of 22
(12)
Turunen, L.; Warzok, U.; Schalley, C. A.; Rissanen, K.
star consisting of six resorcinarene motifs and eight trigo-
nal connectors was constructed in one pot, and its well-
defined architecture was evidenced by the TEM images as
well as the exceptionally sharp 1H NMR signals. This work
presents an efficient self-assembly method for preparation
of cavitand-functionalized nanocapsules with tunable size
and geometry, which are potential candidates for applica-
tions in molecular self-recognition and catalysis.
Nano-sized I12L6 Molecular Capsules Based on the [N⋅⋅⋅I+⋅⋅⋅N]
Halogen Bond. Chem 2017, 3, 861-869.
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2
3
4
5
6
7
(13)
Pei, W. Y.; Xu, G.; Yang, J.; Wu, H.; Chen, B.; Zhou, W.;
Ma, J. F. Versatile Assembly of Metal-Coordinated
Calix[4]resorcinarene Cavitands and Cages through Ancillary
Linker Tuning. J. Am. Chem. Soc. 2017, 139, 7648-7656.
(14)
Shivanyuk, A.; Rebek, J., Jr. Reversible Encapsulation by
Self-Assembling Resorcinarene Subunits. Proc. Natl. Acad. Sci.
U.S.A. 2001, 98, 7662-7665.
8
9
ASSOCIATED CONTENT
Supporting Information.
(15)
Haino, T.; Fukuta, K.; Iwamoto, H.; Iwata, S.
Noncovalent Isotope Effect for Guest Encapsulation in Self-
Assembled Molecular Capsules. Chem. Eur. J. 2009, 15, 13286-
13290.
(16)
Encapsulation and Self-Assembly of
Coordination Capsule. Chem. Eur. J. 2006, 12, 3310-3319.
(17) Tsunoda, Y.; Fukuta, K.; Imamura, T.; Sekiya, R.;
Furuyama, T.; Kobayashi, N.; Haino, T. High Diastereoselection of
a Dissymmetric Capsule by Chiral Guest Complexation. Angew.
Chem. Int. Ed. 2014, 53, 7243-7247.
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The Supporting Information is available free of charge on the
ACS Publications website at DOI:
Haino, T.; Kobayashi, M.; Fukazawa, Y. Guest
Video S1: energy-minimized model of cubic star [Cd24L16L6 ]
8
a
Cavitand-Based
(MOV)
Experimental details and characterization data (PDF)
AUTHOR INFORMATION
Corresponding Author
(18)
Yu, G.; Jie, K.; Huang, F. Supramolecular Amphiphiles
*ytchan@ntu.edu.tw
Notes
The authors declare no competing financial interest.
Based on Host–Guest Molecular Recognition Motifs. Chem. Rev.
2015, 115, 7240-7303.
(19)
Zhou, Y.; Jie, K.; Zhao, R.; Huang, F. Supramolecular-
Macrocycle-Based Crystalline Organic Materials. Adv. Mater.
2019, 1904824.
(20) Zhang, Q.; Tiefenbacher, K. Hexameric Resorcinarene
Capsule is a Bronsted Acid: Investigation and Application to
Synthesis and Catalysis. J. Am. Chem. Soc. 2013, 135, 16213-16219.
(21)
Strukul, G. Efficient Isonitrile Hydration through Encapsulation
within Hexameric Self-assembled Capsule and Selective
Inhibition by a Photo-controllable Competitive Guest. Chem.
Commun. 2013, 49, 5322-5324.
ACKNOWLEDGMENTS
This research was supported by the Ministry of Science and
Technology of Taiwan (MOST106-2628-M-002-007-MY3).
Bianchini, G.; La Sorella, G.; Canever, N.; Scarso, A.;
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85x58mm (300 x 300 DPI)
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TOC Artwork
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