Self-Assembled Perylene Bisimide-Cored Trigonal Prism as an Electron-Deficient Host for C60and C70Driven by "like Dissolves Like"

Article abstract of DOI:10.1021/jacs.0c06623

Poor processability of fullerenes is a major remaining drawback for them to be studied monomolecularly and to find real-life applications. One of the strategies to tackle this problem is to encapsulate them within a host, which is however quite often, accompanied by significant alteration of their physical/chemical properties as encountered in chemical modification. To minimize the effect, an electron-deficient entities-based, dissolvable, and fluorescence active supramolecular host was designed and constructed via coordination-driven self-assembly of o-tetrapyridyl perylene bisimide (PBI) with cis-(PEt3)2Pt(OTf)2. The trigonal prism 1 possesses a trigonal-prismatic inner cavity with 14.7 ? as the diameter of its inscribed circle. Host-guest chemistry investigations revealed that both C60 and C70 could be quantitatively encapsulated by the host in a 1:1 ratio. Further studies demonstrated that the produced host-guest complex 1a?C70 is significantly more stable than 1a?C60, allowing complete transformation of the latter to the former and separation of C70 from its mixture with C60. The fullerenes in the inclusion state could rotate freely within the cavity. Electrochemistry and spectroscopy studies disclosed that the encapsulation of the guests shows little effect upon the reduction of the host and its fluorescence properties. Thus, "like dissolves like"is believed to be the main driving force for the formation of the host-guest complexes. Moreover, the host and host-guest complexes can be fabricated into monomolecular membranes using the conventional Langmuir-Blodgett technique. We propose that these unique host-guest complexes could be used as model ensembles for further studies of the physical/chemical properties of fullerenes in both single molecular and 2D membrane states. In addition, their reversible four-electron reduction property may allow them to find applications in photo/electrocatalysis, organic electronics, etc.

Full text of DOI:10.1021/jacs.0c06623

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Article
Self-assembled Perylene Bisimide-cored Trigonal Prism as an Electron-
deficient Host for C60 and C70 Driven by ‘Like Dissolves Like’
Xingmao Chang, Simin Lin, Gang Wang, Congdi Shang,
Zhaolong Wang, Kaiqiang Liu, Yu Fang, and Peter J. Stang
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 26 Aug 2020
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Self-assembled Perylene Bisimide-cored Trigonal Prism as
an Electron-deficient Host for C60 and C70
Driven by ‘Like Dissolves Like’
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Xingmao Chang,1,2 Simin Lin,1 Gang Wang,1 Congdi Shang,1 Zhaolong Wang,1
Kaiqiang Liu,1 Yu Fang,1,* and Peter J. Stang2,*
1Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical
Engineering, Shaanxi Normal University, Xi’an 710119, P. R. China
2Department of Chemistry, University of Utah, 315 South 1400 East, Room 2020, Salt Lake City, Utah 84112, United States
Abstract Poor processability of fullerenes is a major remaining drawback for them to be studied
monomolecularly and to find real-life applications. One of the strategies to tackle this problem is
to encapsulate them within a host, which is however quite often, accompanied with significant
alteration of their physical/chemical properties as encountered in chemical modification. To
minimize the effect, an electron-deficient entities-based, dissolvable and fluorescence active
supramolecular host was designed and constructed via coordination-driven self-assembly of
ortho-tetrapyridyl perylene bisimide (PBI) with cis-(PEt3)2Pt(OTf)2. The trigonal prism 1
possesses a trigonal-prismatic inner cavity with 14.7 Å as the diameter of its inscribed circle.
Host-guest chemistry investigations revealed that both C60 and C70 could be quantitatively
encapsulated by the host in a 1:1 ratio. Further studies demonstrated that the produced host-guest
complex 1C70 is significantly more stable than 1C60, allowing complete transformation of the
latter to the former and separation of C70 from its mixture with C60. The fullerenes in the inclusion
state could rotate freely within the cavity. Electrochemistry and spectroscopy studies disclosed
that the encapsulation of the guests shows little effect upon the reduction of the host and its
fluorescence properties. Thus, ‘like dissolves like’ is believed to be the main driving force for the
formation of the host-guest complexes. Moreover, the host and host-guest complexes can be
fabricated into monomolecular membranes, using conventional Langmuir-Blodgett technique. We
propose that these unique host-guest complexes could be used as model ensembles for further
studies of the physical/chemical properties of fullerenes in both single molecular and 2D
membrane states. In addition, their reversible four-electron reduction property may allow them to
find applications in photo-/electro-catalysis, organic electronics, etc.
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Introduction
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Coordination-driven self-assembly has been developed as a powerful tool for precise
construction of Supramolecular Coordination Complexes (SCCs) with diverse sizes and shapes,
including 2D metallacycles, 3D metallacages, and even more elegant and complex molecular
assemblies.1-9 Apart from building structures with special shape, large size or unique topology,10-13
development of functional SCCs leading to important applications is also a hot topic of the
research.14-21 A noticeable strategy to achieve such a purpose is to embed selected functional
moieties in the building blocks of SCCs.22-28 Fluorescence is known to be sensitive and selective
to micro-environment changes owing to its excited state nature, and thereby, incorporating
fluorescent moieties will definitely extend the applications of SCCs.17,18 In fact, emissive SCCs
have already been utilized in multi-responsive (solvents, pressure, or temperature) materials,
photodynamic therapy, film-based fluorescence sensors, etc.18, 20, 29-31
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As known, perylene bisimides (PBIs) have received significant attention during the last few
decades owing to their unique properties, such as large optical absorption range, superior
photochemical and thermal stability, high fluorescence quantum yield, switchable emission
between monomeric state and aggregated state.32-34 Yet, they generally suffer from low solubility
in common solvents due to strong intermolecular - stacking originating from large conjugated
structure of their perylene core, which limits the study of their properties and applications.
Therefore, alkyl chains with different lengths or steric structures are often introduced into the
imide or bay positions (3,4,9,10-positions) of PBIs to increase their solubility.35-37 Recently,
selective modification at the ortho-positions (2,5,8,11-positions) of PBIs is also used to improve
the solubility.38-40 Unlike being modified at the bay positions, structural modification at the
ortho-positions shows little distortion to the planar structure of the perylene core, which is believed
to bring less alteration to their electronic structures and the excited state properties.41, 42
As a family of zero-dimensional carbon materials, fullerenes exhibit superior semi-conducting
properties, leading to versatile applications in solar cells, field effect transistors (FET),
photo-detectors, etc.43-45 These applications, however, greatly depend on their purity, crystalline
structures, aggregated geometries, such as 1D fibers, 2D plates, etc. Additionally, well defined
structures are also the basis for exploring their fundamental properties. However, the spherical or
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ellipsoid shape and the unpolarized polyene surfaces greatly hinder their dissolution in common
solvents, impeding their purification, crystallization and property studies in conventional ways. To
tackle the challenge, various strategies, such as volatile diffusion, controlled precipitation,
liquid-liquid interface precipitation, gel-assisted crystallization, etc., have been developed to grow
the crystals or to purify the materials.46-52 Among them, host-guest chemistry-based extraction was
proposed recently, which brings new inclusion compounds with fullerenes as guests, leading to
assisted dissolution as well as new structures. The key issue in the studies is the design and
construction of supramolecular hosts. Till now, a large number of macrocycles and several 3D
cages have been developed as the hosts.53-56 Examination reveals that effective hosts generally
possess two features, the first is size match of their cavities with the guests, fullerenes, and the
second is electronic match of the hosts with the electron-poor guests, as evidenced by the fact that
electron-rich moieties, such as porphyrins, pyrene, anthracenes, tetrathiafulvalenes and carbon
belts/bowls, were adopted as their main components.57-79 However, electronic communication
between electron-rich host and electron-deficient guest is sure to alter the primary properties of the
guest as well as the host, which could induce similar problems encountered as in the chemical
modifications. Therefore, it would be of great interest to develop electron-poor hosts that include
the guests via other driving forces.
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Considering the electron-deficient property and the polyene surface feature of fullerenes,
constructing the expected host-guest complexes via the development of electron-poor hosts with
-conjugated structures, such as PBI derivatives, as the main entities becomes feasible. This is due
to the fact that ‘like dissolves like’ may function as the driving force, which originates from their
common -structure. In addition, incorporating such fluorescence active moieties in the hosts
could offer the opportunity to monitor the coming host-guest interaction via their sensitivity to
micro-environment of changes. As aforementioned, coordination-driven self-assembly is a
powerful technique to build 3D metallacages with controllable sizes and changeable functional
moieties. Thus, it may be adopted as a strategy to build the designed hosts. In fact, several
(supra)molecular cycles or cages composed of PBI moieties have been synthesized via covalent
linkage or noncovalent bonding,80-84 where only one metallacage and one metallacycle have been
built for the encapsulation of fullerenes.62, 78 However, in the hosts, PBIs were modified at the
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bay-positions, leading to distorted structure of the perylene core. To avoid this distortion, in the
present study, an ortho-position modified PBI derivative is incorporated into a specially designed
3D metallacage, resulting in the trigonal prism 1. Encapsulation examination reveals effective
formation of inclusion complexes of 1C60 and 1C70. Further investigation depicts that 1C70 is
more stable than 1C60. Accordingly, selective extraction of C70 from its mixture with C60 and
complex to complex transformation from 1C60 to 1C70 were realized. Weak electronic
communication between the host and the guests is verified by little change of the host’s
electrochemical and spectroscopy properties after encapsulation.
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Scheme 1 Formation of Trigonal Prism 1 via Coordination-Driven Self-Assembly
Results and Discussion
Synthesis of PBI-4Py
Ortho-tetrapyridiyl-containing PBI (3) was targeted to construct trigonal prism 1, and the PBI
derivative was synthesized by coupling of 4-ethynylpyridine with ortho-iodinated PBI (2), where
2 was obtained via carbonyl-directed ortho C-H halogenation of PBI.39 Structural optimization of
3 was performed through DFT calculation. The results are depicted in Figure S21. As expected,
the core of 3 adopts a perfect planar structure, allowing for the construction of well-defined and
non-distorted architecture via coordination-driven self-assembly.
Self-assembly of Trigonal Prism
As shown in Scheme 1, reacting 3 with cis-(PEt3)2Pt(OTf)2 in a molar radio of 2:4 in acetone
o
for 5 h at 45 C, and then precipitating by the addition of diethyl ether resulted in 1 with an
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excellent yield (98%). It is worthwhile to note that reacting of four-arm ligand (L) with Pt/Pd(Ⅱ)
(M) could result in metallo-cages with a composition of M2nLn, where M6L3, M8L4, M10L5, and
even M12L6 have been documented.85-90 In this work, the supramolecular ensemble is confirmed to
9
1
be M6L3, for which the characterization details via multinuclear NMR (31P and H), correlation
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spectroscopy NMR (COSY), diffusion-ordered spectroscopy NMR (DOSY), electrospray
ionization time-of-flight mass spectroscopy (ESI-TOF-MS), etc. are provided below.
Figure 1 (a) Partial 1H NMR spectra (600 MHz, Acetone-d6, 298 K) of 3 (black) and 1 (red). (b)
31P NMR spectra (243 MHz, Acetone-d6, 298 K) of 4 (black) and 1 (red). (c) Experimental (black)
and calculated (red) ESI-TOF-MS spectra of 1 [1 − 5OTf]5+.
As seen from Figure 1b, the 31P{1H} NMR spectrum of 1 shifts considerably upfield comparing
with that of 90° Pt(II) 4 and exhibits sharp singlet at -0.15 ppm with concomitant 195Pt satellites
(JPt−P = 3100.7 Hz), corresponding to single chemical environments around the phosphorus center.
1
For the H NMR spectrum of 3, it can be observed that it contains three sets of protons in the
aromatic area, including two doubles for pyridinyl (δ = 8.74 and 7.65 ppm for H3a and H3b,
1
respectively) and one singlet for PBI moiety (δ = 8.79 ppm for H3c) (Figure 1a). The H NMR
spectrum of 1 exhibits a simple set of proton signals, where the aromatic part is composed of four
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doublets and one singlet, which are ascribable to the protons of pyridinyl moiety and PBI unit,
respectively (Figure S3). The COSY spectra shown in Figure S5 indicate that the 3a and 3b
protons of the pyridinyl moiety exhibit a remarkable split and a significant shift in comparison
with 3. The shift of the proton signals is a result of the nitrogen coordination to Pt since it reduces
the electron density of the pyridyl unit. The splitting of 3a and 3b might be because of restricted
rotation of the pyridinyl moieties due to the formation of the trigonal prism that makes a
difference between the magnetic environment of the two 3a (H1a and H1a’) and the two 3b (H1b and
H1b’) protons of a pyridyl moiety. These observations tentatively reveal the formation of the
expected discrete, highly symmetrical supramolecular cage.
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The DOSY results are depicted in Figure S8. As seen, the sample displays a single vertical trace
with a diffusion coefficient of 4.0 × 10−6 cm2 s−1, suggesting the formation of a single
supramolecular ensemble via self-assembly. With reference to the ESI-TOF-MS spectra shown in
Figure 1c and Figure S7, six isotopically resolved peaks corresponding to a trigonal prism (M6L3)
with the loss of several trifluoromethanesulfonate (OTf) anions were observed, including m/z =
1646.36 for [1−4OTf]4+, m/z = 1287.30 for [1−5OTf]5+, m/z = 1047.93 for [1−6OTf]6+, m/z =
876.94 for [1−7OTf]7+, m/z = 748.58 for [1−8OTf]8+, and m/z = 648.96 for [1−9OTf]9+. These
peaks match very well with the calculated theoretical distributions, and confirm the stoichiometry
of the trigonal prism as produced. Moreover, traces of other possible M2nLn structures are not
observable.
Molecular Modeling and Langmuir-Blodgett Technique
The chemical formula of three ligands and six metals of the trigonal prism has been proved via
NMR and mass spectroscopy measurements. However, as depicted in Scheme 1, 3 is a highly
symmetrical and four-arm ligand, which determines that it could form two isomeric trigonal
prisms when it reacts with 90o Pt in a molar ratio of 1:2. The two structures were simulated via
PM6 semi-empirical calculations. As shown in Figure 2, the only difference between them is the
orientation of the PBI moieties, which makes isomer a possess a larger triangular section.
Specifically, the area of the section for a is 575 Å2, and that for b is 447 Å2 (for calculation
details, see Figure S22 in the SI). Energetically, a is much more stable that b, and the energy
difference between them is 36 kcal/mol. The difference could be a result of the high distortion of
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the PBI units in b and the crowding of the imide parts of the moieties in the isomer. Accordingly,
the most likely structure of the cage as obtained should be a. To exam the exact structure of the
cage, Langmuir−Blodgett (LB) measurements were performed as it could provide the information
of molecular size, which helps to ascertain the structure.
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Considering the good solubility in volatile organic solvents, and insolubility in water of the
cage, it is possible to prepare a monomolecular layer via utilization of the classical LB technique.
The experiments resulted in the -A isotherms, which are the surface pressure vs molecular area
plots that are presented in Figures 2c and Figure S23a.
Figure 2 The PM6-simulated conformation of the trigonal prism of 1 in ‘a’ state (a, c) and the
PM6-simulated conformation of the trigonal prism in ‘b’ state (b). The –A isotherm of the
trigonal prism of 1 in the air/water interface (d).
As depicted in Figure S23, three independent measurements (with the addition of different
volumes of the stock solution of 1) resulted in highly repeatable -A isotherms, indicating the
reliability of the measurements. Examination of the -A isotherms reveals that they all exhibit a
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sharp rise of surface pressure when decreasing the surface area, it can also be seen that the liquid
condensed (LC) phase appears from 2 to 33 mN-1, and the “liquid” to “solid” inflection appears at
33 mN m-1. Further increase of the surface pressure results in the collapse of the “solid”
mono-molecular membrane as evidenced by the gradual appearance of a precipitation on the
slider. (Figure S23b) From the inflection point, the area of cross-section (A) of 1 can be calculated
using eq. 1, where S stands for the total surface area of the membrane, C the concentration of the
solution, V the volume of the solution added, and NA is Avogadro's number. The result is about
569 Å2/molecule, which matches well with the area of the triangle side of conformation a as
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shown in Figures 2c and S22.
푆
퐴 = 퐶푉푁
(1)
퐴
Fullerenes Host-Guest Encapsulation
1
Figure 3 31P{1H} (a-c) and partial H NMR spectra (d-f) of 1 (a and d), 1C60 (b and e), and
1C70 (c and f). (243 MHz for 31P{1H}NMR and 600 MHz for 1H NMR, Acetone-d6, 298 K)
The existence of large void and electron deficient PBI moieties in the trigonal prism could
create two different environments, where one is inside and the other outside of the metallacage.
Examination of the size of the cavity as shown in Figure 2 reveals that a sphere or cylinder of a
maximum diameter of 14.7 Å could be embedded within the cavity, suggesting that the compound
may be used as a host for encapsulation of C60 and C70 since the van der Waals diameter of the
former is ~11 Å and the latter a little bit larger.70, 73, 76 Encapsulation tests were conducted by
adding a large excess of C60 or C70 (10 equiv) to a solution of 1 in acetone, followed by continuous
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heating and stirring at 40 °C overnight. The solution was filtered to remove excess C60 or C70, and
then precipitated by adding ethyl ether. Acetone was chosen as it is a good solvent of the host but
a poor solvent of the guests.91 The precipitates (possibly 1C60 or 1C70) were collected by
centrifugation, and characterized by NMR and ESI-TOF-MS measurements.
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Figure 4 Partial 13C NMR spectra (151 MHz, Acetone-d6, 298 K) of 1 (a), 1C60 (b), and 1C70
(c). Note:  stands for 13C signal of C60 or C70.
As depicted in Figure 3, similar to that of the host, the 31P{1H} NMR spectrum of 1C60 is also
characterized by a sharp singlet, which shifted downfield to 0.30 ppm, indicating a change of the
chemical environment of the phosphorus center. The 31P{1H} NMR could be a result of the
expected encapsulation, which is further supported by the results from 1H NMR studies. As shown
in the same figure, comparing the 1H NMR spectrum of 1C60 with that of 1, the proton signals of
pyridinyl residues (H1a, H1a′; H1b′, H1b) in the PBI structures show an upfield shift in support of the
possible host-guest interaction. The protons of PBI (H1c) show a considerable downfield shift from
9.21 to 9.31, which is almost mixed with one of the pyridinyl signals (H1a′). This observation
could be ascribed to the - interaction between PBI and C60, another evidence to support the
host-guest interaction. The 13C NMR spectra of 1C60 and empty 1 were also recorded (Figure 4a,
b). An intense extra resonance signal appears at 141.6 ppm, which belongs to C60, further
confirming formation of the expected host-guest complex, 1C60, due to the fact that C60 alone is
insoluble in the solvent. ESI-TOF-MS spectra of 1C60 are depicted in Figure 5c and Figure S13,
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displaying a series of prominent peaks at m/z = 1826.36, 1431.50, 1168.09, 979.50, 838.70, and
728.96, which correspond to the loss of several OTf units during ionization, including
[1C60-4OTf]4+, [1C60-5OTf]5+, [1C60-6OTf]6+, [1C60-7OTf]7+, [1C60-8OTf]8+, and
[1C60-9OTf]9+, respectively. These m/z results match very well with the theoretically simulated
values, in support of the expected 1:1 composition of the host-guest complex. Further examination
of the results depicted in Figure 5 reveals that there are weak signals of the empty trigonal prism
in the sample of the host-guest complex, suggesting dissociation of 1C60 during the ionization
measurements.
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1
C70 was also expected to form an inclusion complex 1C70. 31P{1H} NMR, H NMR and 13C
NMR spectra exhibit the formation of the complex (Figure 3, Figure 4c), but the proton signal of
PBI shifts obviously upfield rather than downfield as observed in the complexation of C60. The
reason behind is probably the different interaction with the hosts as the size and shape of the two
guests are different from each other. The difference in the proton signal shift of PBI can be used to
identify the two different fullerenes. Results from ESI-TOF-MS provide further support for
possible inclusion. As shown in Figure 5 and Figure S18, six isotopically resolved peaks, which
are 1856.61 ([1C70-4OTf]4+), 1455.50 ([1C70-5OTf]5+), 1187.93 ([1C70-6OTf]6+), 996.94
([1C70-7OTf]7+), 853.71 ([1C70-8OTf]8+) and 742.31 ([1C70-9OTf]9+), respectively,
corresponding to 1C70 after losing four to nine OTf units were detected, confirming the
stoichiometry of the expected host-guest complex. Examination of the results depicted in Figure 5
reveals that unlike 1C60, there is no empty trigonal prism in the sample, indicating effective
encapsulation of C70, which indicates no significant dissociation of 1C70 during the ionization
measurements.
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Figure 5 Partial mass spectra monitoring the formation of host-guest complexes with loss of seven
(a) and five (b) OTf. Experimental (black) and calculated (red) ESI-TOF-MS spectra of 1C60
[1C60 − 5OTf]5+ (c) and 1C70 [1C70 − 5OTf]5+ (d).
DOSY studies of the two host-guest complexes in acetone-d6 were also performed, and the
results are shown in Figure S14 and Figure S20, respectively. As shown, the diffusion coefficients
of 1C60 and 1C70 are all close to 4.0 × 10−6 cm2 s−1, which are almost the same as that of empty
1, indicating that complexation shows little effect upon the size of the host, an evidence of internal
inclusion rather than external association.
Further examination of the 13C NMR spectra depicted in Figure 4 reveals that 1C60 shows
only one 13C NMR signal (Figure 4b: 141.6 ppm), whereas 1C70 shows five (Figure 4c: 149.43
ppm, 146.33 ppm, 145.86 ppm, 143.41 ppm and 128.83 ppm), which are consistent with the
70
numbers of carbon types of the relevant fullerenes.57,
These results may be taken as an
indication that the guests are trapped within an isotropic electromagnetic field, which however is,
not the case, due to complicated internal structure of the host. However, a possible rationalization
of the results is to assume free rotation of the guests within the cavity of the host, due to the weak
electronic communication between the guest and the host.
Competitive Encapsulation of C60 and C70
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To gain insight on the timescale of the exchange between host and host-guest complex, empty
cage 1 was respectively added into the acetone-d6 solution of 1C60 and 1C70 (in 10% and 30%),
and then the solution was continuously stirred for 5 hours. As shown in Figure S24, both signals
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of free host and complexes exist in their H NMR and 31P{1H} NMR spectra, indicating that the
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exchange is slow. Competitive encapsulation tests of C60 and C70 were also performed, which may
provide information about the comparative affinities of the host to the guests.
The mixture of 1C60 and large excess of C70 (10 equiv), and vice versa, the mixture of 1C70
and large excess of C60 (10 equiv) in acetone-d6 were mixed and stirred for 5 hours at 45 °C. Then,
1
the H NMR spectra of the two systems were recorded. The results are depicted in Figures 6a-c
and S25, respectively. As seen, the introduction of C70 resulted in complete disappearance of the
characteristic proton signal (9.31 ppm) of 1C60 and the appearance of that (9.13 ppm) of 1C70,
indicating full transformation of 1C60 to 1C70. The result from the replacement test of C60 to
1
1C70, is in support of this conclusion as there is no observable change in the recorded H NMR
spectra, even though a large excess of C60 was added. Therefore, it might be concluded that the
binding affinity of the trigonal prism toward C70 is much larger than that toward C60.
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Figure 6 Cartoons for complex transformation from 1C60 to 1C70 (a) and selective extraction
1
of C70 from its mixture with C60 (d), and the corresponding partial H NMR spectra of the
processes before (c) and after (b) the transformation, as well as before (f) and after (e) the
separation.( 600 MHz, Acetone-d6, 298 K)
Given the different binding affinity of the host to C60 and C70, its potential in their separation
was briefly explored. A mixture of C60 and C70 was added to the acetone-d6 solution of 1, and then
1
the mixture was stirred 5 hours at 40 °C. H NMR spectrum of the supernatant solution was
recorded (Figures 6d-f), and only 1C70 was observed as the H1c signal appears at 9.13 ppm, a
beacon of the complex, suggesting potential application of the prepared host in separation of C70
from its mixture with C60.
1
The H NMR measurements of 1C60 and 1C70 in very low concentrations were also
1
conducted to further check the stability of complexes (Figure S26). It is seen that the H NMR
spectra are still dominated by the signals of 1C60 and 1C70, and there is no observable signals
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of the free cage, indicating good stability of the host-guest complexes.
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Electrochemistry Study
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Both PBI and fullerenes (C60 and C70) are electron-deficient conjugated systems and could
undergo reversible electrochemical oxidation and reduction.62, 68 To understand the property of the
host and the host-guest complex, cyclic voltammetry (CV) and square wave voltammetry (SWV)
were performed on 1, 1C60, 1C70 and the relevant PBI derivative 3. The specific parameters of
the systems and the electrochemical traces are given in Table 1 and Figure S27. As seen, 3
exhibits two reversible reductions at -0.85 and -1.08 V, respectively, which could originate from
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푒
successive reductions of the PBI core (PBI 푒 PBI− PBI2−).61 As akin to other shoulder substituted
PBI derivatives, oxidation is not found within the examined electrochemical widow.39 For only 1,
two reversible reduction processes around -0.61 and -0.81 V are observed, which are from the
reduction of the PBI core. However, compared to the reference, reduction of PBI in the host
becomes easier, which could be a result of coordination to the platinum center.
a, b
Table 1 Redox potentials of 3, 1, 1C60, and 1C70
a All measurements were performed in dry CH3CN except for 3 (CH2Cl2) with 0.1 M n-Bu4NPF6
as electrolyte. b The data presented were obtained from square wave voltammetry measurements.
In the CV and SWV of 1C60, four reduction processes are found, where the initial two are
associated with the PBI units (-0.59 and -0.77 V), and the third and fourth (-1.05 and -1.21 V)
푒
푒
−
could be successive reductions of the guest (C60 C60 C602−). As seen, encapsulation of the guest
shows limited effect upon the reduction of the PBI units, confirming weak electronic
communication between the guest and the host, as tentatively already concluded from the 13C
NMR studies. Similar results were obtained in the examination of 1C70. These results further
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confirm the formation of the host-guest complexes.
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Optical Properties
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Figure 7 UV-Vis (a) and fluorescence (b) spectra of 1, 1C60, and 1C70 in acetone, where the
excitation wavelength adopted is 480 nm.
UV-Vis absorption, fluorescence, and fluorescence lifetimes of 1, 1C60 and 1C70 were also
measured, and the results are provided in Figure 7 and Figure S28. In the UV-Vis absorption
spectra, it is seen that the spectrum of 1 contains two characteristic monomeric absorption bands
of the PBI unit, appearing at ~531 nm and ~495 nm, respectively, which are ascribable to the 0-0
and 0-1 absorptions of the S0-S1 transition, respectively. The second is the vibronic progression of
the main absorption band resulting from the coupling of the electronic transition to the
C-C-stretching modes of the perylene core. The ratio of the intensities of the 0-0 and 0-1
absorption bands (A0-0/A0-1) is ~1.56, further suggesting a monomeric nature of PBI units in the
host, which is commonly used to monitor the aggregation of the PBI moiety.32 This result can be
taken as an additional evidence to support the framework structure of the host, ruling out packing
both inter- and intramolecularly. Inclusion of C60 resulted in the red-shift of the spectrum with
little change in the profile and the ratio of A0-0/A0-1, again confirming the weak interaction
between the host and the guest, since little effect is observed for the coupling between the
electronic transition and the PBI core. For 1C70, a similar result is observed. The only difference
is more significant red-shift, which could be a result of a closer contact of C70 with the PBI
moieties in the host due to its larger size. This result is in agreement with that aforementioned in
the 1H NMR, 13C NMR and electrochemical studies.
To gain further insight into the electronic communication between the guests and the PBI
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moieties in the host, their fluorescence spectra were also recorded in dilute condition in acetone
(1.010-5 mol/L) to minimize the reabsorption effect. The results are depicted in Figure 7b. Cage 1
shows a fluorescence spectrum characteristic for the PBI monomers with an emission maximum at
~541 nm and well-resolved vibronic fine structures, which is a mirror-image of the absorption of
the PBI unit. In addition, a small Stokes shift of 10 nm and a relatively high fluorescence quantum
yield of 0.20 were observed, which are in support that the PBI moieties exist in a monomeric state
within the host.
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In contrast, the fluorescence emission spectra of the two host-guest complexes, especially that
of 1C70, show observable changes in the profiles as the relative intensity of the first band (short
wavelength) to the second one decreases with the complexation, which is a result of re-absorption
since the Stokes shifts are getting narrower from 1 to 1C60 and then to 1C70. However, the
monomeric feature of the PBI moieties in the complexes still remains, not only because of their
slightly-changed UV-Vis absorptions, but also because of their similar emission profiles. These
results further demonstrate that the inclusion of C60 or C70 shows limited effect upon the electronic
nature of the host and, likewise, upon the guests, an expected result but different with that reported
by Beer et al.77 Fluorescence lifetime measurements further support these conclusions as the
fluorescence decay curves of the PBIs moieties in the three systems are very similar to each other,
and their lifetimes are almost the same (Figure S28, Table S1).
Combining the results from the electrochemical and optical studies with those from the
encapsulation experiments, we can conclude that the examined host-guest interaction is mainly
driven by the so called ‘like dissolves like’ principle. Size matching may further stabilize the
complexes. In other words, the cavity property of the dissolved hosts could be very different from
that of the bulk medium, acetone, as it is characterized by delocalized electrons due to the
conjugated structures of the PBI moieties. It is exactly this property that makes the host function
as microdomains in the solution, leading to preponderant affinity to fullerenes and, thus, resulting
in the observed encapsulation.
Conclusion
In conclusion, a fluorescent SCC, trigonal prism 1, was synthesized via coordination-driven
self-assembly of tetrapyridinyl perylene bisimides and 90° organoplatinum(II) in a molar ratio of
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1:2. The structure of 1 was confirmed by various techniques, including H NMR, 31P{1H} NMR,
13C NMR, COSY, DOSY, and high-resolution mass spectrometry, and further studied by
structural simulation and the Langmuir-Blodgett technique. As designed, 1 possesses a
trigonal-prismatic cavity that makes it suitable for encapsulation of C60 and C70, which may be
owing to the ‘like dissolves like’ principle. The formation of the host-guest complexes of 1C60
and 1C70 was verified by using the same methods. Further studies revealed that 1 exhibits a
greater binding affinity toward C70 than C60, and the encapsulated C60 and C70 could rotate freely
within the cavity of the host. Electrochemical studies demonstrated that 1C60 and 1C70 possess
a four-electron accepting property. We suggest that the generated electron-deficient entities-based,
dissolvable, fluorescence active host-guest complexes will not only allow detailed studies of the
physical and chemical properties of the caged fullerenes in single molecular and 2D membrane
states, but also further investigation of applications of these unique host-guest complexes in a
variety of fields, such as photo-/electro-catalytic processes, organic electronics, etc.
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Author information
Corresponding Authors
*yfang@snnu.edu.cn
*stang@chem.utah.edu
Notes
The authors declare no competing financial interest.
Acknowledgements
This work was supported by the Natural Science Foundation of China (21527802, 21673133,
21872091, 21820102005), 111 project (B14041), Program for Changjiang Scholars and
Innovative Research Team in University (IRT-14R33). X. C. thanks Drs. Yan Sun, Zaiwen Yang
and Yiliang Wang for extensive helpful discussions, Ms. Juan Fan for discussion on ESI-TOF-MS
experiments, and Miss Xiaohua (Sophie) Fang for linguistic assistance during the preparation of
this manuscript.
References
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5
1. Fujita, M.; Tominaga, M.; Hori, A.; Therrien, B. Coordination assemblies from a
Pd(II)-cornered square complex. Acc. Chem. Res. 2005, 38, 371-380.
6
7
8
9
2. Cook, T. R.; Zheng, Y. R.; Stang, P. J. Metal-organic frameworks and self-assembled
supramolecular coordination complexes: comparing and contrasting the design, synthesis,
and functionality of metal-organic materials. Chem. Rev. 2013, 113, 734-777.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3. Mukherjee, S.; Mukherjee, P. S. Template-free multicomponent coordination-driven
self-assembly of Pd(II)/Pt(II) molecular cages. Chem. Commun. 2014, 50, 2239-2248.
4. Cook, T. R.; Stang, P. J. Recent developments in the preparation and chemistry of
metallacycles and metallacages via coordination. Chem. Rev. 2015, 115, 7001-7045.
5. Newkome, G. R.; Moorefield, C. N. From 13 dendritic designs to fractal
supramacromolecular constructs: understanding the pathway to the Sierpinski gasket. Chem.
Soc. Rev. 2015, 44, 3954-3967.
6. Clever, G. H.; Punt, P. Cation-anion arrangement patterns in self-assembled Pd2L4 and Pd4L8
coordination cages. Acc. Chem. Res. 2017, 50, 2233-2243.
7. Fielden, S. D. P.; Leigh, D. A.; Woltering, S. L. Molecular knots. Angew. Chem. Int. Ed.
2017, 56, 11166-11194.
8. Saha, S.; Regeni, I.; Clever, G. H. Structure relationships between bis-monodentate ligands
and coordination driven self-assemblies. Coordin. Chem. Rev. 2018, 374, 1-14.
9. Sun, Y.; Chen, C.; Liu, J.; Stang, P. J. Recent developments in the construction and
applications of platinum-based metallacycles and metallacages via coordination. Chem. Soc.
Rev., 2020, 49, 3889-3919.
10. Danon, J. J.; Krüger, A.; Leigh, D. A.; Lemonnier, J.-F.; Stephens, A. J.; Vitorica-Yrezabal,
I. J.; Woltering, S. L. Braiding a molecular knot with eight crossings. Science, 2017, 355,
159-162.
11. Fujita, D.; Ueda, Y.; Sato, S.; Mizuno, N.; Kumasaka, T.; Fujita, M. Self-assembly of
tetravalent goldberg polyhedra from 144 small components. Nature 2016, 540, 563-566.
12. Fujita, D.; Ueda, Y.; Sato, S.; Yokoyama, H.; Mizuno, N.; Kumasaka, T.; Fujita, M.
Self-assembly of M30L60 icosidodecahedron. Chem 2016, 1, 91-101.
13. Wang, H.; Liu, C. H.; Wang, K.; Wang, M.; Yu, H.; Kandapal, S.; Brzozowski, R.; Xu, B.;
Wang, M.; Lu, S.; Hao, X. Q.; Eswara, P.; Nieh, M. P.; Cai, J.; Li, X. Assembling pentatopic
terpyridine ligands with three types of coordination moieties into a giant supramolecular
hexagonal prism: synthesis, self-assembly, characterization, and antimicrobial study. J. Am.
Chem. Soc. 2019, 141, 16108-16116.
14. Yoshizawa, M.; Klosterman, J. K.; Fujita, M. Functional molecular flasks: new properties
and reactions within discrete, self-assembled hosts. Angew. Chem. Int. Ed. 2009, 48,
3418-3438.
15. Brown, C. J.; Toste, F. D.; Bergman, R. G.; Raymond, K. N. Supramolecular catalysis in
18 / 25
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Page 19 of 25
Journal of the American Chemical Society
1
2
3
4
metal-ligand cluster hosts. Chem. Rev. 2015, 115, 3012-3035.
5
6
7
16. Chen, K.; Shu, Q.; Schmittel, M. Design strategies for lab-on-a-molecule probes and
orthogonal sensing. Chem. Soc. Rev. 2015, 44, 136-160.
8
9
17. Yam, V. W.-W.; Au, V. K.-M.; Leung, S. Y.-L. Light-emitting self-assembled materials
based on d8 and d8 transition metal complexes. Chem. Rev. 2015, 115, 7589-7728.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
18. Saha, M. L.; Yan, X.; Stang, P. J. Photophysical properties of organoplatinum(II) compounds
and derived self-assembled metallacycles and metallacages: fluorescence and its applications.
Acc. Chem. Res. 2016, 49, 2527-2539.
19. Roberts, D. A.; Pilgrim, B. S.; Nitschke, J. R. Covalent post-assembly modification in
metallosupramolecular chemistry. Chem. Soc. Rev. 2018, 47, 626-644.
20. Sepehrpour, H.; Fu, W.; Sun, Y.; Stang, P. J. Biomedically relevant self-assembled
metallacycles and metallacages. J. Am. Chem. Soc. 2019, 141, 14005-14020.
21. Sun, Y.; Chen, C.; Stang, P. J. Soft materials with diverse suprastructures via the
self-assembly of metal-organic complexes. Acc. Chem. Res. 2019, 52, 802-817.
22. Cao, L.; Wang, P.; Miao, X.; Dong, Y.; Wang, H.; Duan, H.; Yu, Y.; Li, X.; Stang, P. J.
Diamondoid supramolecular coordination frameworks from discrete adamantanoid
Platinum(II) cages. J. Am. Chem. Soc. 2018, 140, 7005-7011.
23. Sun, Y.; Li, S.; Zhou, Z.; Saha, M. L.; Datta, S.; Zhang, M.; Yan, X.; Tian, D.; Wang, H.;
Wang, L.; Li, X.; Liu, M.; Li, H.; Stang, P. J. Alanine-based chiral metallogels via
supramolecular coordination complex platforms: metallogelation induced chirality transfer. J.
Am. Chem. Soc. 2018, 140, 3257-3263.
24. Shi, B.; Zhou, Z.; Vanderlinden, R. T.; Tang, J. H.; Yu, G.; Acharyya, K.; Sepehrpour, H.;
Stang, P. J. Spontaneous supramolecular polymerization driven by discrete Platinum
metallacycle-based host-guest complexation. J. Am. Chem. Soc. 2019. 141, 11837-11841.
25. Yan, X.; Cook, T. R.; Wang, P.; Huang, F.; Stang, P. J. Highly emissive Platinum(II)
metallacages. Nature Chem. 2015, 7, 342-348.
26. Zhou, Z.; Chen, D. G.; Saha, M. L.; Wang, H.; Li, X.; Chou, P. T.; Stang, P. J. Designed
conformation and fluorescence properties of self-assembled phenazine-cored Platinum(II)
metallacycles. J. Am. Chem. Soc. 2019, 141, 5535-5543.
27. Li, G.; Zhou, Z.; Yuan, C.; Guo, Z.; Liu, Y.; Zhao, D.; Liu, K.; Zhao, J.; Tan, H.; Yan, X.
Trackable supramolecular fusion: cage to cage transformation of tetraphenylethylene-based
metalloassemblies. Angew. Chem. Int. Ed. 2020, 59, 10013-10017.
28. Zhang, Z.; Zhao, Z.; Wu, L.; Lu, S.; Ling, S.; Li, G.; Xu, L.; Ma, L.; Hou, Y.; Wang, X.; Li,
X.; He, G.; Wang, K.; Zou, B.; Zhang, M. Emissive Platinum(II) cages with reverse
fluorescence resonance energy transfer for multiple sensing. J. Am. Chem. Soc. 2020, 142,
2592-2600.
29. Tang, J. H.; Sun, Y.; Gong, Z. L.; Li, Z. Y.; Zhou, Z.; Wang, H.; Li, X.; Saha, M. L.; Zhong,
19 / 25
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Journal of the American Chemical Society
Page 20 of 25
1
2
3
4
5
Y. W.; Stang, P. J. Temperature-responsive fluorescent organoplatinum(II) metallacycles. J.
Am. Chem. Soc. 2018, 140, 7723-7729.
6
7
8
9
30. Zhou, Z.; Liu, J.; Huang, J.; Rees, T. W.; Wang, Y.; Wang, H.; Li, X.; Chao, H.; Stang, P. J.
A self-assembled Ru-Pt metallacage as a lysosome-targeting photosensitizer for 2-photon
photodynamic therapy. Proc. Natl. Acad. Sci. U. S. A. 2019, 116, 20296-20302.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
31. Chang, X.; Zhou, Z.; Shang, C.; Wang, G.; Wang, Z.; Qi, Y.; Li, Z. Y.; Wang, H.; Cao, L.;
Li, X.; Fang, Y.; Stang, P. J. Coordination-driven self-assembled metallacycles incorporating
pyrene: fluorescence mutability, tunability, and aromatic amine sensing. J. Am. Chem. Soc.
2019, 141, 1757-1765.
32. Würthner, F.; Saha-Moller, C. R.; Fimmel, B.; Ogi, S.; Leowanawat, P.; Schmidt, D.
Perylene bisimide dye assemblies as archetype functional supramolecular materials. Chem.
Rev. 2016, 116, 962-1052.
33. Chen, S.; Slattum, P.; Wang, C.; Zang, L. Self-assembly of perylene imide molecules into 1D
nanostructures: methods, morphologies, and applications. Chem. Rev. 2015, 115,
11967-11998.
34. Yang, Z.; Chen, X. Semiconducting perylene diimide nanostructure: multifunctional
phototheranostic nanoplatform. Acc. Chem. Res. 2019, 52, 1245-1254.
35. Kang, R.; Miao, R.; Qi, Y.; Chang, X.; Shang, C.; Wang, L.; Fang, Y. Tuning the formation
of reductive species of perylene-bisimide derivatives in DMF via aggregation matter. Chem.
Commun. 2017, 53, 10018-10021.
36. Liu, K.; Shang, C.; Wang, Z.; Qi, Y.; Miao, R.; Liu, K.; Liu, T.; Fang, Y. Non-contact
identification and differentiation of illicit drugs using fluorescent films. Nature Commun.
2018, 9, 1695.
37. Wang, Z.; Wang, G.; Chang, X.; Liu, K.; Qi, Y.; Shang, C.; Huang, R.; Liu, T.; Fang, Y. A
perylene bisimide-contained molecular dyad with high-efficient charge separation:
switchability, tunability, and applicability in moisture detection. Adv. Funct. Mater. 2019, 29,
1905295.
38. Battagliarin, G.; Li, C.; Enkelmann, V.; Müllen, K. 2,5,8,11-Tetraboronic ester
perylenediimides: a next generation building block for dye-stuff synthesis. Org. Lett. 2011,
13, 3012-3015.
39. Wu, J.; He, D.; Zhang, L.; Liu, Y.; Mo, X.; Lin, J.; Zhang, H. J. Direct synthesis of
large-scale ortho-iodinated perylene diimides: key precursors for functional dyes. Org. Lett.
2017, 19, 5438-5441.
40. Nowak-Król, A.; Würthner, F. Progress in the synthesis of perylene bisimide dyes. Org.
Chem. Front. 2019, 6, 1272-1318.
41. Yu, Z.; Wu, Y.; Liao, Q.; Zhang, H.; Bai, S.; Li, H.; Xu, Z.; Sun, C.; Wang, X.; Yao, J.; Fu,
H. Self-assembled microdisk lasers of perylenediimides. J. Am. Chem. Soc. 2015, 137,
15105-15111.
20 / 25
ACS Paragon Plus Environment

Page 21 of 25
Journal of the American Chemical Society
1
2
3
4
5
6
42. Zeng, C.; Xiao, C.; Feng, X.; Zhang, L.; Jiang, W.; Wang, Z. Electron-transporting
bis(heterotetracenes) with tunable helical packing. Angew. Chem. Int. Ed. 2018, 57,
10933-10937.
7
8
43. Park, S. K.; Kim, J. H.; Park, S. Y. Organic 2D optoelectronic crystals: charge transport,
9
emerging functions, and their design perspective. Adv. Mater. 2018, 30, e1704759.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
44. Yang, F.; Cheng, S.; Zhang, X.; Ren, X.; Li, R.; Dong, H.; Hu, W. 2D organic materials for
optoelectronic applications. Adv. Mater. 2018, 30, 1702415.
45. Yang, Y.; Li, G. Progress in high-effcient solution process organic photovoltaic devices,
Springer-Verlag, Berlin/Heidelberg, Germany 2015.
46. Nair, V. S.; Mukhopadhyay, R. D.; Saeki, A.; Seki, S.; Ajayaghosh, A. A -gel scaffold for
assembling fullerene to photoconducting supramolecular rods. Sci. Adv. 2016, 2, e1600142.
47. Geng J.; Zhou, W.; Skelton, P.; Yue, W.; Kinloch, I. A.; Windle, A. H.; Johnson, B. F. G.
Crystal structure and growth mechanism of unusually long fullerene (C60) nanowires. J. Am.
Chem. Soc. 2008, 130, 2527-2534.
48. Wu, K. Y.; Wu, T. Y.; Chang, S. T.; Hsu, C. S.; Wang, C. L. A facile PDMS-assisted
crystallization for the crystal-engineering of C60 single-crystal organic field-effect transistors.
Adv. Mater. 2015, 27, 4371-4376.
49. Cui, D.; Ebrahimi, M.; Rosei, F.; Macleod, J. M. Control of fullerene crystallization from 2D
to 3D through combined solvent and template effects. J. Am. Chem. Soc. 2017, 139,
16732-16740.
50. Yan, W.; Qu, Y.; Gupta, T. D.; Darga, A.; Nguyên, D. T.; Page, A. G.; Rossi, M.; Ceriotti,
M.; Sorin, F. Semiconducting nanowire-based optoelectronic fibers. Adv. Mater. 2017, 29,
1700681.
51. Lee, K.; Choi, B.; Plante, I. J.; Paley, M. V.; Zhong, X.; Crowther, A. C.; Owen, J. S.; Zhu,
X.; Roy, X. Two-dimensional fullerene assembly from an exfoliated van der Waals template.
Angew. Chem. Int. Ed. 2018, 57, 6125-6129.
52. Liu, K.; Gao, S.; Zheng, Z.; Deng, X.; Mukherjee, S.; Wang, S.; Xu, H.; Wang, J.; Liu, J.;
Zhai, T.; Fang, Y. Spatially confined growth of fullerene to super-long crystalline fibers in
supramolecular gels for high-performance photodetector. Adv. Mater. 2019, 31, e1808254.
53. Tashiro, K.; Aida, T. Metalloporphyrin hosts for supramolecular chemistry of fullerenes.
Chem. Soc. Rev. 2007, 36, 189-197.
54. Pérez, E. M.; Martín, N. Curves ahead: molecular receptors for fullerenes based on
concave-convex complementarity. Chem. Soc. Rev. 2008, 37, 1512-1519.
55. Canevet, D.; Pérez, E. M.; Martín, N. Wraparound hosts for fullerenes: tailored macrocycles
and cages. Angew. Chem. Int. Ed. 2011, 50, 9248-9259.
56. García-Simón, C.; Costas, M.; Ribas, X. Metallosupramolecular receptors for fullerene
binding and release. Chem. Soc. Rev. 2016, 45, 40-62.
21 / 25
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 22 of 25
1
2
3
4
5
6
57. Yanagisawa, M.; Tashiro, K.; Yamasaki, M.; Aida, T. Hosting fullerenes by dynamic bond
formation with an iridium porphyrin cyclic dimer:ꢀ a “chemical friction” for rotary guest
motions. J. Am. Chem. Soc. 2007, 129, 11912-11913.
7
8
58. Suzuki, K.; Takao, K.; Sato, S.; Fujita, M. Coronene nanophase within coordination spheres:
9
increased solubility of C60. J. Am. Chem. Soc. 2010, 132, 2544-2545.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
59. Huerta, E.; Isla, H.; Pérez, E. M.; Bo, C.; Martín, N.; de Mendoza, J. Tripodal exTTF-CTV
hosts for fullerenes. J. Am. Chem. Soc. 2010, 132, 5351-5353.
60. Song, J.; Aratani, N.; Shinokubo, H.; Osuka, A. A porphyrin nanobarrel that encapsulates
C60. J. Am. Chem. Soc. 2010, 132, 16356-16357.
61. Iwamoto, T.; Watanabe, Y.; Sadahiro, T.; Haino, T.; Yamago, S. Size-selective encapsulation
of C60 by [10]cycloparaphenylene: formation of the shortest fullerene-peapod. Angew. Chem.
Int. Ed. 2011, 50, 8342-8344.
62. Mahata, K.; Frischmann, P. D.; Würthner, F. Giant electroactive M4L6 tetrahedral host
self-assembled with Fe(II) vertices and perylene bisimide dye edges. J. Am. Chem. Soc. 2013,
135, 15656-15661.
63. Nakamura, T.; Ube, H.; Miyake, R.; Shionoya, M. A C60-templated tetrameric porphyrin
barrel complex via zinc-mediated self-assembly utilizing labile capping ligands. J. Am.
Chem. Soc. 2013, 135, 18790-18793.
64. Kishi, N.; Akita, M.; Yoshizawa, M. Selective host-guest interactions of a transformable
coordination capsule/tube with fullerenes. Angew. Chem. Int. Ed. 2014, 53, 3604-3607.
65. Yokoi, H.; Hiraoka, Y.; Hiroto, S.; Sakamaki, D.; Seki, S.; Shinokubo, H.
Nitrogen-embedded buckybowl and its assembly with C60. Nature Commun. 2015, 6, 8215.
66. Brenner, W.; Ronson, T. K.; Nitschke, J. R. Separation and selective formation of fullerene
adducts within an MII L6 cage. J. Am. Chem. Soc. 2017, 139, 75-78.
8
67. Ke, X. S.; Kim, T.; Lynch, V. M.; Kim, D.; Sessler, J. L. Flattened calixarene-like cyclic
BODIPY array: a new photosynthetic antenna model. J. Am. Chem. Soc. 2017, 139,
13950-13956.
68. Rizzuto, F. J.; Wood, D. M.; Ronson, T. K.; Nitschke, J. R. Tuning the redox properties of
fullerene clusters within a metal-organic capsule. J. Am. Chem. Soc. 2017, 139, 11008-11011.
69. Kawano, S. I.; Fukushima, T.; Tanaka, K. Specific and oriented encapsulation of fullerene
C70 into a supramolecular double-decker cage composed of shape-persistent macrocycles.
Angew. Chem. Int. Ed. 2018, 57, 14827-14831.
70. Shi, Y.; Cai, K.; Xiao, H.; Liu, Z.; Zhou, J.; Shen, D.; Qiu, Y.; Guo, Q. H.; Stern, C.;
Wasielewski, M. R.; Diederich, F.; Goddard, W. A., III; Stoddart, J. F. Selective extraction of
C70 by a tetragonal prismatic porphyrin cage. J. Am. Chem. Soc. 2018, 140, 13835-13842.
71. Takeda, M.; Hiroto, S.; Yokoi, H.; Lee, S.; Kim, D.; Shinokubo, H. Azabuckybowl-based
molecular tweezers as C60 and C70 receptors. J. Am. Chem. Soc. 2018, 140, 6336-6342.
22 / 25
ACS Paragon Plus Environment

Page 23 of 25
Journal of the American Chemical Society
1
2
3
4
5
6
72. Xu, Y.; Wang, B.; Kaur, R.; Minameyer, M. B.; Bothe, M.; Drewello, T.; Guldi, D. M.; von
Delius, M. A Supramolecular [10]CPP junction enables efficient electron transfer in modular
porphyrin-[10]CPP fullerene complexes. Angew. Chem. Int. Ed. 2018, 57, 11549-11553.
7
73. Chen, B.; Holstein, J. J.; Horiuchi, S.; Hiller, W. G.; Clever, G. H. Pd(II) coordination sphere
engineering: pyridine cages, quinoline bowls, and heteroleptic pills binding one or two
fullerenes. J. Am. Chem. Soc. 2019, 141, 8907-8913.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
74. Huang, Q.; Zhuang, G.; Jia, H.; Qian, M.; Cui, S.; Yang, S.; Du, P. Photoconductive
curved-nanographene/fullerene supramolecular heterojunctions. Angew. Chem. Int. Ed. 2019,
58, 6244-6249.
75. Lu, X.; Gopalakrishna, T. Y.; Han, Y.; Ni, Y.; Zou, Y.; Wu, J. Bowl-shaped carbon nanobelts
showing size-dependent properties and selective encapsulation of C70. J. Am. Chem. Soc.
2019, 141, 5934-5941.
76. Martinez-Agramunt, V.; Eder, T.; Darmandeh, H.; Guisado-Barrios, G.; Peris, E. A
size-flexible organometallic box for the encapsulation of fullerenes. Angew. Chem. Int. Ed.
2019, 58, 5682-5686.
77. Nakamura, T.; Tsukuda, S.; Nabeshima, T. Double-circularly connected Saloph-belt
macrocycles generated from a bis-armed bifunctional monomer. J. Am. Chem. Soc. 2019,
141, 6462-6467.
78. Barendt, T. A.; Myers, W. K.; Cornes, S. P.; Lebedeva, M. A.; Porfyrakis, K.; Marques, I.;
Félix, V.; Beer, P. D. The green box: an electronically versatile perylene diimide macrocyclic
host for fullerenes. J. Am. Chem. Soc. 2020, 142, 349-364.
79. Fuertes-Espinosa, C.; García-Simón, C.; Pujals, M.; Garcia-Borràs, M.; Gómez, L.; Parella,
T.; Juanhuix, J.; Imaz, I.; Maspoch, D.; Costas, M.; Ribas, X. Supramolecular fullerene
sponges as catalytic masks for regioselective functionalization of C60. Chem 2020, 6,
169-186.
80. Würthner, F.; Sautter, A. Highly fluorescent and electroactive molecular squares containing
perylene bisimide ligands. Chem. Commun. 2000, 445-446.
81. You, C. C.; Hippius, C.; Grune, M.; Würthner, F. Light-harvesting metallosupramolecular
squares composed of perylene bisimide walls and fluorescent antenna dyes. Chem. Eur. J.
2006, 12, 7510-7519.
82. Frischmann, P. D.; Kunz, V.; Stepanenko, V.; Würthner, F. Subcomponent self-assembly of a
4 nm M4 L6 tetrahedron with Zn(II) vertices and perylene bisimide dye edges. Chem. Eur. J.
2015, 21, 2766-2769.
83. Frischmann, P. D.; Kunz, V.; Würthner, F. Bright fluorescence and host-guest sensing with a
nanoscale M4L6 tetrahedron accessed by self-assembly of Zinc-imine chelate vertices and
perylene bisimide edges. Angew. Chem. Int. Ed. 2015, 54, 7285-7289.
84. Sapotta, M.; Hofmann, A.; Bialas, D.; Würthner, F. A water-soluble perylene bisimide
cyclophane as a molecular probe for the recognition of aromatic alkaloids. Angew. Chem. Int.
23 / 25
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 24 of 25
1
2
3
4
Ed. 2019, 58, 3516-3520.
5
6
7
8
85. Bhat, I. A.; Jain, R.; Siddiqui, M. M.; Saini, D. K.; Mukherjee P. S. Water-soluble Pd8L4
self-assembled molecular barrel as an aqueous carrier for hydrophobic curcumin. Inorg.
Chem. 2017, 56, 5352-5360.
9
86. Bivaud, S.; Balandier, J. -Y.; Chas, M.; Allain, M.; Goeb, S.; Sallé, M. A metal-directed
self-assembled electroactive cage with bis(pyrrolo)tetrathiafulvalene (BPTTF) side walls. J.
Am. Chem. Soc. 2012, 134, 11968-11970.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
87. Cecot, G.; Marmier, M.; Geremia, S.; De Zorzi, R.; Vologzhanina, A. V.; Pattison, P.; Solari,
E.; Fadaei, F. T.; Scopelliti, R.; Severin, K. The intricate structural chemistry of MII2nLn-type
assemblies. J. Am. Chem. Soc. 2017, 139, 8371- 8381.
88. Cecot, G.; Alameddine, B.; Prior, S.; De Zorzi, R.; Geremia, S.; Scopelliti, R.; Fadaei, F.
T.; Solari, E.; Severin, K. Large heterometallic coordination cages with gyrobifastigium-like
geometry. Chem. Commun. 2016, 52, 11243-11246.
89. Bhat, I. A.; Devaraj A.; Zangrando E.; Mukherjee, P. S. A discrete self‐assembled Pd12
triangular orthobicupola cage and its use for intramolecular cycloaddition. Chem. Eur. J.
2018, 24, 13938-13946.
90. Yang, J.; Bhadbhade, M.; Donald, W. A.; Iranmanesh, H.; Moore, E. G.; Yan, H.; Beves, J.
E. Self-assembled supramolecular cages containing Ruthenium(II) polypyridyl complexes.
Chem. Commun. 2015, 51, 4465-4468.
91. Semenov, K. N.; Charykov, N. A.; Keskinov, V. A.; Piartman, A. K.; Blokhin, A. A.;
Kopyrin, A. A. Solubility of light fullerenes in organic solvents. J. Chem. Eng. Data 2010,
55, 13-36.
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Self-assembled Perylene Bisimide-cored Trigonal Prism as
an Electron-deficient Host for C60 and C70
Driven by ‘Like Dissolves Like’
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Xingmao Chang,1,2 Simin Lin,1 Gang Wang,1 Congdi Shang,1 Zhaolong Wang,1
Kaiqiang Liu,1 Yu Fang,1,* and Peter J. Stang2,*
1Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical
Engineering, Shaanxi Normal University, Xi’an 710119, P. R. China
2Department of Chemistry, University of Utah, 315 South 1400 East, Room 2020, Salt Lake City, Utah 84112, United States
TOC
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