Control of Heterometallic Three-Dimensional Macrocycles with Aromatic Stacks in Tunable Host Cavities

Article abstract of DOI:10.1002/cjoc.201800121

Using coinage metal (Cu(II), Ag(I)) hinges, two sets of heterometallic molecular capsules with analogous open-ended cavities were prepared based on the half-sandwich rhodium fragments. In the case of [Rh₄Cu₄] cages, up to six-fold-stacked host-guest structures were formed by varying the cavity's dimensions. Moreover, the series of capsules were demonstrated to self-fine-tune to form multi-heteroguest arrays via favourable donor-acceptor π interactions and Ag-π interactions, as evidenced from single-crystal X-ray analysis.

Full text of DOI:10.1002/cjoc.201800121

Cite this paper: Gao, W.-X.; Fan, Q.-J.; Lin, Y.-J.; Jin, G.-X. Chin. J. Chem. 2018, 36, 594－598.
Breaking Report
DOI: 10.1002/cjoc.201800121
Control of Heterometallic Three-Dimensional Macrocycles with Aromatic
Stacks in Tunable Host Cavities
a
a
a
,a
Wen-Xi Gao, Qi-Jia Fan, Yue-Jian Lin, and Guo-Xin Jin*
ABSTRACT Using coinage metal (Cu(II), Ag(I)) hinges, two sets of heterometallic molecular capsules with analogous open-ended cavities were prepared
based on the half-sandwich rhodium fragments. In the case of [Rh Cu ] cages, up to six-fold-stacked host-guest structures were formed by varying the
4
4
cavity’s dimensions. Moreover, the series of capsules were demonstrated to self-fine-tune to form multi-heteroguest arrays via favourable donor-acceptor
π interactions and Ag-π interactions, as evidenced from single-crystal X-ray analysis.
KEYWORDS host-guest chemistry, open-ended cavity, heterometallic capsule, half-sandwich rhodium fragments
Introduction
Scheme 1 Two multidentate ligands with distinct coordination modes
and binuclear metalloligands Cu (dppd) , [Ag (Hdmppd) ][OTf]
2
2
2
2
2
Natural spontaneous and precise self-assembly of functional
superstructures inspires the mimicking of analogues. Enzymes,
nature’s masterpiece, provide molecular-sized and specific-shaped
pockets capable of selectively binding substrates and effectively
catalysing unique reactions. Alternatively, so-called host-guest ca-
talysis is regarded as a conventional route to produce artificial
[
1]
molecular flasks. Molecular capsules constructed by non-cova-
lent interactions could offer well-defined local microenvironment
trapping the guests within the cavities. Well-matched geometries
of cavity and guest, as well as well-defined host-guest interactions,
are both crucial to bind substrates in a predictable array or aggre-
[
2,3]
gation manner.
The pre-programming of smaller building blocks to come to-
gether to form more advanced assemblies has been extensively
[4,5]
used
in the construction of artificial molecular flasks to encap-
sulate small molecules. Thereby, strategic selection of rigid organ-
ic ligands and exploitation of the specific coordination geometries
of metal centres are regarded as the basic design principles of
stable confined cavities, resulting in closed box-shaped molecular
capsules, which lack “windows” for guest release and catalysis
turnover. This property contrasts with the structures of most nat-
ural vehicles, for which selected release and capture phenomena
are frequently observed, restricting its further application.
Herein, a series of heterometallic supramolecular coordina-
tion capsules capable of anchoring aromatic guests in open-ended
cavities by coinage metals centres Cu(II) and Ag(I) are presented.
The assemblies have similar geometries but bind the aromatic
guest molecules through completely different approaches. The
stepwise manner from binuclear macrocyclic metalloligand
[
Cu
Cp*＝η -pentamethylcyclopentadienyl, 1.0 equiv.) was treated
SCF ) (4.0 equiv.), followed by the addition of
bidentate ligand Na [Cu(opba)] [opba＝1,2-phenylenebis(oxam-
ate)] (1.0 equiv.) in methanol. The resulting solution was then
treated with Cu (bddp) (1.0 equiv.) to form the capsule complex
in a yield of 75.4%.
Slow vapor diffusion of diethyl ether into a methanol/tetrahy-
2
(bddp) ], as shown in Scheme 2. A solution of [Cp*RhCl ]
2
2
2
5
(
with AgOTf (Tf＝O
2
3
2
2
2
1
drofuran solution of 1 yielded single crystals suitable for X-ray
diffraction analysis, confirming the open-ended cage-like frame-
work of 1 in the solid state (Figure 1a). As expected, a pair of pla-
nar dicopper building blocks were bridged by rigid linear metal-
dicopper building block Cu
2 2 2
(bddp) (H bddp＝3,5-bis(1,3-dioxo-
4
,4-dimethylpentyl)pyridine) shown in Scheme 1, known to act as
2

[
6]
loligand Cu(opba) in a 1 :1 molar ratio, whereby the four Cp*Rh
fragments occupy the vertices, forming a [Rh Cu ] heterometallic
an electron-deficient metalloligand, was used to construct a
series of heterometallic cages in a stepwise manner. Discrete sex-
tet-stacking host-guest structures were formed by utilizing fa-
vourable donor-acceptor (D-A) π interactions. Furthermore, in-
spired by the geometry of the cages with embedded copper(II)
centres, silver-containing heterometallic molecular containers
were constructed in good yields, templated by stacks of multiple
coronene units. The aromatic guests were found to be anchored
in the open-ended cavity by Ag-π interactions, which was demon-
strated by single-crystal X-ray analysis.
4
6
cage with an open-ended cavity. It was observed that one of the
originally unsaturated copper cations from each dicopper plane
was found to be coordinated to one tetrahydrofuran molecule
inside the cavity, while another copper centre was coordinated by
a molecule of methanol on the outside of the assembly.
Owing to the utilization of the dicopper(II)-containing plat-
form, known to act as an electron-deficient surface, the cavity of
cage 1 was initially investigated as an aromatic guest receptor,
which was expected to interact with the aromatic moieties
through aromatic donor-acceptor π interactions. In order to verify
the guest-binding ability, a slight excess of electron-rich aromatic
Results and Discussion
The [Rh
4
Cu
6
] heterometallic macrocage 1 was constructed in a
1
coronene (G ) was introduced to the solution of cage 1. The
a
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,
State Key Laboratory of Molecular Engineering of Polymers, Collaborative In-
novation Center of Chemistry for Energy Materials, Department of Chemistry,
Fudan University, Shanghai 200433, China
*E-mail: gxjin@fudan.edu.cn
594
© 2018 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2018, 36, 594－598

Control of Heterometallic Three-Dimensional Macrocycles with Aromatic Stacks
Chin. J. Chem.
Scheme 2 Stepwise construction of the heterometallic capsule from metalloligand Cu
2
(bddp)
2
and the encapsulation of multi-heteroguest staking arrays
obtained UV-Vis spectra showed only minimal changes upon
guest binding, and the fluorescence of the coronene moieties was
largely quenched by the Cp*Rh fragments in the cages; hence,
these techniques were not used to investigate guest binding in
solution. However, the solid-state structure of the host-guest ad-
duct was unambiguously demonstrated by X-ray diffraction analy-
sis (Figure 1b). The capsule framework was observed to dilate to
accommodate the double-stacked coronene molecules, where-
upon the distance between two opposite copper centres in-
creased to 9.95 Å from 7.37 Å. The duplex aromatic staking array
was established by a π-π interaction with an average separation of
3
.4 Å (Figure S10, Table S1 in the Supporting Information). More-
over, the stronger intermolecular binding of the aromatic coro-
nene molecules and the electron deficient surface of the capsule
resulted in complete displacement of the coordinated tetrahy-
drofuran in favour of the stacked coronene molecules.
Figure 1 X-ray crystal structures of cationic parts of (a) the tetrahydrofu-
ran adduct of heterometallic cage 1; (b) coronene-encapsulated cage 1.
Hydrogen atoms, OTf anions and coordinated methanol molecules are

omitted for clarity (N, blue; O, red; C, gray; Rh, pink; Cu, turquoise).
To reach the full potential of the aromatic donor-acceptor π
interactions between cavity and guest molecules, an attempt was
made to wedge a π-electron acceptor guest, N,N'-dimethyl-
allowing quintet stacking with a favourable average distance of
3.36 Å.
1
,4,5,8-naphthalene-tetracarboxylic diimide (G
2
), in between the
In light of the encouraging synthesis of quintet stacking com-
plexes, larger stacks were predicted to arise from analogous en-
capsulation in cavities of appropriately increased size. The longer
bidentate ligand 4,4'-bis(dipyrromethan-5-yl)biphenyl (bdpmbp)
was chosen to bridge two electron-deficient surfaces with a dis-
tance of 17.06 Å (Rh···Rh non-bonding distance). Gratifyingly, the
results of single-crystal X-ray analysis revealed that a four-layer
guest array was captured inside the open-ended cavity, as shown
in Figure 2b. The distance between two opposite copper centres
increased to 16.87 Å from 13.44 Å in the case of guest adduct 2,
resulting in an average interplanar distances of 3.4 Å. This indi-
cated a very close packing of the π-donor and -acceptor units in
the A-D-A-A-D-A sextet inclusion complex 3 (Figure S11, Table S2
in the Supporting Information).
two aromatic molecules, in order to form a larger multiply-
stacked inclusion complex. As expected, the cages, given their
adaptable void volumes via strategic selection of different bridg-
ing ligands, were found to be capable of encapsulating hetero-
guest quintet and sextet stacks inside perfectly size-matched cavi-
ties, as unambiguously determined by single-crystal X-ray diffrac-
tion analysis.
2
As shown in Figure 2a, one electron-deficient G guest was
found to be sandwiched between two coronene molecules, which
were further encapsulated in the cavity of the cage, forming the
well-defined quintet stacking complex 2. The two dicopper planes
bridged by 1,4-bis(dipyrromethan-5-yl)benzene (bdpmb) ligands
were found to be 13.44 Å apart (Cu···Cu non-bonding distance),
Chin. J. Chem. 2018, 36, 594－598
© 2018 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
595

Breaking Report
Gao et al.
ments were placed at the bottom of a culture tube, followed by
careful layering of a diethyl ether and hexane solution of coro-
nene. The crystallographic analysis confirmed the host-guest
structure of 4 as shown in Figure 3.
Figure 2 X-ray crystal structures of cationic parts of (a) quintet stacking
complex 2; (b) sextet stacking host-guest adduct 3. Hydrogen atoms and
−
OTf anions are omitted for clarity (N, blue; O, red; C, gray; Rh, pink; Cu,
turquoise).
Figure 3 X-ray crystal structure of cationic parts of (a) 4; (b) 5. Hydrogen
atoms and OTf anions are omitted for clarity (N, blue; O, red; C, gray; Rh,

pink; Ag, orange).
Inspired by the encapsulation of multiple guests in the large
cavity of heterometallic cage 3, another coinage metal, silver(I),
was selected to serve as an anchor to bind aromatic guests inside
similar molecular capsules, which would possess analogous nano-
cavities to the copper(II)-containing cages described above. Such
an assembly would take advantage of metal−π interactions, a
well-known class of bonding between metal centres and aromatic
systems, and has been utilized to facilitate the formation of a
In the resulting structure, two coronene molecules were in-
cluded in the cavity via relatively weak Ag-π interactions with an
average distance of 3.2 Å between the silver(I) centres and the
coronene plane (Figure S12 in the Supporting Information), re-
sulting in a Ag-π-π-Ag arrangement. Two N－Ag－N angles in the
same disilver plane were found to be ca. 170.0° and 174.7°, re-
spectively. Moreover, multipoint CH-π interactions between the
coronene and the lateral bridging ligands appear to stabilize the
complex, with CH-π distances of around 2.75 Å.
[
3a,7]
wide range of metal-arene complexes.
Scheme 3 Construction of [Rh
4 4
Ag ] heterometallic adducts 4 and 5 from
Subsequently, we explored the ability of the capsule to en-
capsulate larger multi-aromatic arrays. For instance, the silver-
containing binuclear building block reacts with one equivalent of
dinuclear Cp*Rh fragments bridged by trans-1,2-bis(4-pyridyl)eth-
ene in the presence of a slight excess of coronene, affording a
light-yellow precipitate of 5 in the dark. Structural authentication
metalloligand [Ag (Hdmppd) ][OTf]
2
2
2
of 5 confirmed its expected [Rh
b, each Cp*Rh(III) vertex is coordinated by one nitrogen atom
from a trans-1,2-bis(4-pyridyl)ethene linker and one (O,O′) che-
lating site of the deprotonated [Ag (Hdmppd) ][OTf] plane,
4 4
Ag ] structure. As shown in Figure
3
2
2
2
whereby four monovalent silver cations serve as hinges, thus
forming a cage framework with an open-ended cavity. In the re-
sulting structure, a triplet stack of aromatic coronene molecules
2
was found to reside in the cavity of capsule 5 via η -type Ag-π
interaction at the edge of the benzene ring, as shown in Figure
S12 in the Supporting Information. Although the separation of
opposite Ag···Ag atoms is 14.6 Å, which is a little large for the
encapsulation of three aromatic planes, the capsule structure is
somewhat distorted and the distance between the two disilver
planes is decreased to ca. 13.1 Å. Interestingly, the opposite oc-
1 2
curs in the aforementioned complex (G ) ⊂1, where the distance
between opposite copper centres increases to satisfy the triplet
stacking requirements. The change of the cavity size in the pro-
cess of accommodating guest molecules indicates that the flexi-
bility of both sets of capsules, provided by the metal (Cu(II), Ag(I))
hinges in the bridge positions, allows the capsule to fine-tune the
size of the cavity to maximize its interaction with the multiple
stacking arrays inside its nanocavity. In addition, the silver-hinged
heterometallic adduct 5 was found to further connect in an in-
The ligand 1,3-di(3-pyridyl)propane-1,3-dionato (Hdmppd,
Scheme 1) was utilized to coordinate with one equivalent of silver
cations to form a binuclear macrocycle, which could be used as
a building block to construct silver(I)-containing molecular cap-
sules with open-ended cavities as shown in Scheme 3. The reac-
[
8]
2 2 2
tion of macrocyclic building block [Ag (Hdmppd) ][OTf] , 4,4'-
[
8,9]
bipyridine-bridged binuclear Cp*Rh fragments and coronene in
methanol led to a light-yellow precipitate (4). Although initial
attempts to reveal the structure of 4 in solution by detailed NMR
studies were fruitless due to its extremely poor solubility, the
solid-state structure of complex 4 was unambiguously confirmed
by X-ray crystallographic analysis.
termolecular fashion via argentophilic interactions,
forming a
one-dimensional network as shown in Figure S13 in the Support-
ing Information.
Conclusions
Single crystals suitable for X-ray analysis were grown by a het-
In summary, we present herein two sets of heterometallic
molecular capsules with similar open-ended cavities, which are
demonstrated to be suitable hosts for the encapsulation of aro-
erogeneous layer diffusion method in the dark, where a CH
3
OH
solution of [Ag (Hdmppd) ][OTf] and the Cp*Rh-containing frag-
2
2
2
596
www.cjc.wiley-vch.de
© 2018 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2018, 36, 594－598

Control of Heterometallic Three-Dimensional Macrocycles with Aromatic Stacks
matic heteroguests. Remarkably, incorporation of coinage metal
Chin. J. Chem.
for 6 h and then filtered, followed by addition of 4,4'-bipyridine
[
Cu(II), Ag(I)] hinges enable the capsules to self-fine-tune to cap-
ture multiple heteroguests inside their nanocavity, leading to sta-
ble multi-stacked arrays. Furthermore, in the case of [Rh Cu
(7.8 mg, 0.05 mmol). [Ag
coronene (G ) (30 mg, 0.1 mmol) were added to the above solu-
tion and the mixture was stirred at room temperature for 24 h.
The light yellow precipitate was washed by diethyl ether and
hexane. (yield 96.1 mg, 89.6%). Elemental analysis calcd for
2 2 2
(Hdmppd) ][OTf] (48 mg, 0.05 mmol) and
1
4
4
]
cages, up to six-fold-stacked host-guest structures were formed by
utilizing favourable D-A π interactions. Our results thus present a
simple model of the creation and control of supramolecular ar-
chitectures with open-ended cavities, which can further accom-
modate multiply-stacked arrays through various interactions. We
predict that these results will have an impact on the strategies
used in the design of future molecular containers and functional
nanovehicles.
C
168 4 24 12 4 8
H148Ag F N O25Rh S : C 47.03, H 3.48, N 3.92; found C 47.17,
H 3.54, N 3.79.
Preparation of 5. AgOTf (51.4 mg, 0.2 mmol) was added to a
solution of [Cp*RhCl ] (31 mg, 0.05 mmol) in CH OH (10 mL) at
2
2
3
room temperature. The reaction mixture was stirred in the dark
for 6 h and then filtered, followed by addition of trans-1,2-bis(4-
pyridyl)ethene (9.1 mg, 0.05 mmol). [Ag
2 2 2
(Hdmppd) ][OTf] (48 mg,
0
.05 mmol) and coronene (G ) (45 mg, 0.15 mmol) were added to
1
Experimental
Preparation of 1. AgOTf (51.4 mg, 0.2 mmol) was added to a
2 2 3
solution of [Cp*RhCl ] (31 mg, 0.05 mmol) in CH OH (10 mL) at
room temperature. The reaction mixture was stirred in the dark
for 6 h and then filtered, followed by addition of a solution of
the above solution and the mixture was stirred at room tempera-
ture for 24 h. The light yellow precipitate was washed by diethyl
ether and hexane (yield 101.5 mg, 87.3%). Elemental analysis
calcd (%) for C196
found C 50. 47, H 3.66, N 3.42.
Crystallographic details. Single crystals of 1, (G
and 5 suitable for X-ray diffraction study were obtained at room
temperature. X-ray intensity data of 1, (G ⊂1 and 2, 3 were
collected on a Bruker D8 VENTURE system at 150 K and 173 K,
respectively, data of 4 was collected on a CCD-Bruker SMART
APEX system at 173 K, data of 5 was collected on a Bruker D8
VENTURE system at 173 K. In these data, the disordered solvent
molecules which could not be restrained properly were removed
using the SQUEEZE route. The single-crystal X-ray diffraction data
4 24 12 4 8
H170Ag F N O25Rh S : C 50.64, H 3.69, N 3.62;
Na
suspension was kept stirring at room temperature for 6 h and
then [Cu (bddp) ] (39.3 mg, 0.05 mmol) in CH OH (5 mL) was
2 3
[Cu(opba)] (17.9 mg, 0.05 mmol) in CH OH (5 mL), and the
1 2
) ⊂1, 2, 3, 4
2
2
3
1 2
)
added to the mixture. After stirring for another 12 h at room
temperature, the solvent was concentrated to about 3 mL and
diethyl ether was added, to give 1 as green solid (yield 70.6 mg,
7
5.4%). IR (KBr) ν: 3499, 2960, 1617, 1589, 1454, 1414, 1374,

1
1
259, 1226, 1163, 1032, 786, 757, 640, 574, 519 cm . Analysis
160: C 44.91, H 4.31, N 2.99; found
calcd for C140Cu
C 44.72, H 4.26, N 2.85.
Preparation of (G
was added to a solution of the complex 1 (93.6 mg, 0.025 mmol)
in CH OH (10 mL) and the mixture was stirred at room tempera-
6 12 4 4 8
F S O40Rh N H
of 1, (G
1 2
) ⊂1, 2, 3, 4 and 5 have been deposited in the Cambridge
1 2 1
) ⊂1. Coronene (G ) (18.0 mg, 0.06 mmol)
Crystallographic Data Centre under accession number CCDC:
1
1
825020 (1), 1825022 ((G
825018 (4), 1825019 (5).
1 2
) ⊂1), 1825023 (2), 1825021 (3),
3
ture for 6 h. After filtration, the solution was concentrated (3 mL)
and diethyl ether was added to precipitate the solid (yield 91.2 mg,
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.201800121.
8
1
3.9 %). IR (KBr) ν: 3482, 1601, 1560, 1497, 1434, 1388, 1373,
256, 1225, 1160, 1031, 758, 639, 574, 517 cm . Analysis calcd
184: C 51.97, H 4.27, N 2.58; found C

1
6 12 4 4 8
for C188Cu F S O40Rh N H
5
1.72, H 4.38, N 2.41.
Preparation of 2. AgOTf (30.6 mg, 0.12 mmol) was added to a
solution of [Cp*Rh] (bdpmb)Cl (45.4 mg, 0.05 mmol) in CH OH
10 mL) at room temperature and stirred in dark for 6 h, followed
by filtration and [Cu (bddp) ] (39.3 mg, 0.05 mmol) was added,
and the mixture was stirred for another 12 h. Coronene (G ) (15
mg, 0.06 mmol) and G (7.4 mg, 0.025 mmol) were added to the
Acknowledgement
2
2
3
(
This work was supported by the National Natural Science
Foundation of China (Nos. 21531002, 21720102004) and the
Shanghai Science Technology Committee (No. 13JC1400600).
Guo-Xin Jin thanks the Alexander von Humboldt Foundation for a
Humboldt Research Award.
2
2
1
2
above solution and the mixture was stirred at room temperature
for 6 h. After filtration, the solution was concentrated (3 mL) and
diethyl ether was added to precipitate the green solid (yield 108.2
mg, 83.2%). IR (KBr) ν: 3443, 2958, 2917, 2848, 1663, 1603, 1552,
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(
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5
4
374, 1340, 1282, 1248, 1154, 1029, 992, 887, 761, 717, 637, 571,

1
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solution of [Cp*RhCl (31 mg, 0.05 mmol) in CH OH (10 mL) at
room temperature. The reaction mixture was stirred in the dark
4 12 4 4 16
F S O36Rh N H236: C 60.25, H
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Manuscript received: March 14, 2018
Manuscript revised: April 5, 2018
Lahc, M. S.; Chi, K.-W. Chem. Commun. 2015, 51, 4492; (d) Lu, Y.; Lin,
Y.-J.; Li, Z.-H.; Jin, G.-X. Chin. J. Chem. 2018, 36, 106; (e) Lu, Y.; Deng,
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Manuscript accepted: April 19, 2018
Accepted manuscript online: XXXX, 2018
Version of record online: XXXX, 2018
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