A Straightforward Strategy for Constructing Zirconium Metallocavitands

Article abstract of DOI:10.1021/acs.cgd.0c01561

Metallocavitands (MCs), a new burgeoning class of functional multimetallic molecules with specific cavities, are considered as promising materials in many fields. However, designing and constructing metallocavitands with compatibility and tunability from

Full text of DOI:10.1021/acs.cgd.0c01561

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A Straightforward Strategy for Constructing Zirconium
Metallocavitands
Shunfu Du, Xuying Yu, Guoliang Liu, Mi Zhou, EI-Sayed M. El-Sayed, Zhanfeng Ju, Kongzhao Su,
and Daqiang Yuan*
Cite This: Cryst. Growth Des. 2021, 21, 692−697
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ABSTRACT: Metallocavitands (MCs), a new burgeoning class of
functional multimetallic molecules with specific cavities, are
considered as promising materials in many fields. However,
designing and constructing metallocavitands with compatibility
and tunability from simple ligands is highly challenging. In this
work, a series of Zr-based MCs with three distinct structural types
have been prepared based on in situ generated trinuclear
zirconocene (Cp3Zr3) secondary building blocks (SBBs) and V-
shaped dicarboxylic linkers. First, a novel window-shaped Zr-based
MC, namely ZrMC-1, has been constructed based on four Cp3Zr3
SBBs and six simple isophthalate linkers. Its window size and environment could be easily modified by different functional groups,
including nitro (−NO2) and amino (−NH2). Interestingly, the amino-functionalized one, ZrMC-1-NH2, can serve as a robust
heterogeneous cascade catalyst to effectively catalyze the one-pot tandem deacetalization−Knoevenagel condensation reactions.
Second, with the introduction of a sulfonic (−SO3H) group, an unprecedented bowel-like Zr-based MC, namely ZrMC-2,
comprising three Cp3Zr3 SBBs and four 5-sulfoisophthalate ligands, has been obtained. Unexpectedly, one sulfonic group of the
ligand coordinates to the Cp3Zr3 SBB, forming the base of ZrMC-2. Finally, an unexpected zigzag-shaped MC denoted as ZrMC-3
has been prepared by using 2,5-thiophenedicarboxylic acids, featuring a larger bend angle than that of the isophthalate-type one.
Specifically, ZrMC-3 contains two Zr-based prisms with three Cp3Zr3 SBBs and four 2,5-thiophenedicarboxylate linkers; the bottoms
of these two prisms are bridged by another 2,5-thiophenedicarboxylate linker. These results highly suggest that Cp3Zr3 can be an
excellent SBB to construct MCs with fascinating architectures and properties by merely varying the organic linkers.
to construct stable organometallic half-sandwich MCs from
simple and readily accessible ligands for their practical
applications.
1. INTRODUCTION
Metallocavitands (MCs), an emerging class of functional
cavernous compounds, have attracted considerable interest in
the past decades due to their structural beauty and their
promising applications in chemical sensing, separation, host−
guest chemistry, molecular reactors, and so on.1−4 Varieties of
MCs based on different metal ions/clusters and organic linkers
have been well developed.5−9 These MCs can be specifically
divided into six categories based on either a macrocycle-
templating or self-assembly strategy, including flexible macro-
cycle-templated, Schiff base macrocycle-templated, noble metal
N-donor assembled, paddlewheel, miscellaneous metallacrown,
and organometallic half-sandwich MCs.1 In particular, the
organometallic half-sandwich MCs with distinct structural
characteristics, in which metal centers were blocked by
cyclopentadienyl (Cp), pentamethylcyclo-pentadienyl (Cp*),
or arene (CnHm) ligands,10−12 are amenable to form discrete
structures. To date, several organometallic half-sandwich MCs,
assembled from RuII−CnHm, RhIII−Cp*, IrIII−Cp*, ZrIV−Cp,
and TaV−Cp* half-sandwich complexes, have been re-
ported.13−17 However, such MCs require a tightly designed
ligand with high compatibility. Therefore, it is highly desirable
It has been found that the sandwich complex, bis-
(cyclopentadienyl)zirconium dichloride (Cp2ZrCl2), can be
slowly hydrolyzed in water and carboxylic acid simultaneously,
forming near-C3-symmetric Cp3Zr3 clusters, whose one side is
blocked by three Cp ligands, and the other side is coordinated
by three carboxylate ligands.18 With this in mind, our group
initially reported that Cp3Zr3 clusters could be excellent
secondary building blocks (SBBs) in the construction of Zr-
based tetrahedrons by using rigid linear dicarboxylate and
trigonal tricarboxylate linkers.19 Notably, we have also
corroborated that these Zr-based tetrahedrons show excellent
stability in neutral, acidic, and even weak basic aqueous
Received: November 17, 2020
Revised: December 7, 2020
Published: December 22, 2020
https://dx.doi.org/10.1021/acs.cgd.0c01561
© 2020 American Chemical Society
Cryst. Growth Des. 2021, 21, 692−697
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environments.20 Since then, numerous Zr-based polyhedrons,
including tetrahedron, hexahedron, lantern-shaped, and cigar-
like cages built from Cp3Zr3 SBBs, have been developed
(Scheme 1a)21−26 and exhibited potential applications in many
tetramethyl terephthalate,32 which prevents the formation of
the previously reported tetrahedral structure. However, the
systematic preparation, characterization, and applications of
Cp3Zr3-based MCs by using linkers with specific shapes have
not been reported.
Scheme 1. (a) Molecular Topology of the Reported
Coordination Polyhedra, Including Tetrahedron, Lantern,
Cigar, And Hexahedron, Based on Cp3Zr3 SBBs; (b)
Molecular Topology of Zr-Based MCs, Including Window-
Shaped, Bowel-Like, And Zigzag-Shaped Structures, in This
2. EXPERIMENTAL SECTION
2.1. Materials and Instrumentation. All solvents, including
N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF),
carbon tetrachloride (CCl4), methanol (MeOH), reagent Cp2ZrCl2,
isophthalic acid (H2BDC), 5-nitroisophthalic acid (H2BDC-NO2), 5-
aminoisophthalic acid (H2BDC-NH2), sodium 3,5-dicarboxybenzene-
sulfonate (H2BDC−SO3Na), and thiophene-2,5-dicarboxylic acid
(H2TDB), were provided by commercial sources and used without
further purification. Elemental analyses for C, H, and N were
performed on an Elementar Vario MICRO elemental analyzer.
Fourier transform infrared (FT-IR) spectra of the samples were
recorded on KBr pellets in the 4000−400 cm−1 range using a
PerkinElmer Spectrum One FT-IR spectrometer. The powder X-ray
diffraction (PXRD) patterns are collected by a Rigaku DMAX 2500
X-ray diffractometer using Cu Kα radiation (λ = 0.154 nm). All gas
sorption isotherm measurements were performed by using automatic
volumetric adsorption equipment (BeiShiDe 3H-2000PS1).
a
Work
2.2. Synthesis. ZrMC-1. Excess Cp2ZrCl2 (0.015 g) and H2BDC
(0.005 g) were dissolved in a mixture of 1 mL of DMF and 3 drops of
distilled water, and the mixture was then heated at 45 °C for 10 h.
After the mixture slowly cooled down to room temperature, colorless
block crystals were obtained. IR (KBr pellet, cm−1): 3350, 1609, 1550,
1456, 1408, 1274, 1072, 1018, 815, 746, 709, 615, 474. Elemental
analysis (%): calculated for ZrMC-1·18DMA·3H2 O
(Zr12C180N18O61H264Cl4): C, 38.39; H, 5.41; N, 5.17. Found: C,
38.33; H, 5.45; N, 5.1.
ZrMC-1-NO2. Excess Cp2ZrCl2 (0.015 g) and H2BDC−NO2 (0.005
g) were dissolved in a mixture of 1 mL of DMF, 1 mL of MeOH, and
3 drops of distilled water, and the mixture was then heated at 45 °C
for 10 h. After the mixture slowly cooled down to room temperature,
colorless block crystals were obtained. IR (KBr pellet, cm−1): 3350,
1654, 1610, 1566, 1465, 1388, 1348, 1082, 1016, 815, 785, 723, 711,
609, 513, 476. Elemental analysis (%): calculated for ZrMC-1-NO2·
11DMF·CH3OH·H2O (Zr12C142N17O65 H173Cl4): C, 38.9; H, 3.9; N,
5.4. Found: C, 37.5; H, 3.9; N, 5.4.
a
Color code: Cp3Zr3 SBBs, red; linker, blue; sullfonate, yellow.
fields, such as gas storage, catalysis, guest encapsulation, energy
storage, and so on.27−35 However, the reported types of
Cp3Zr3-based coordination complexes are limited to the above-
mentioned polyhedrons based on ditopic and tritopic ligands.
Thus, there is much room to create Cp3Zr3-based complexes
with different architectures by choosing ligands with different
shapes.
In this work, five novel Zr-based MCs with three distinct
structural types, including three window-shaped, bowel-like,
and zigzag-shaped structures, have been developed based on in
situ generated Cp3Zr3 SBBs and V-shaped dicarboxylate linkers
(Scheme 1b). To the best of our knowledge, most of the
reported Zr-based MCs are bowel-shaped and constructed by
using one Cp3Zr3 SBB as a base and three monocarboxylate
ligands as a wall.36,37 Besides, there is only one triangular-
shaped Zr-based MC based on the geometrically frustrated
ZrMC-1-NH2. Excess Cp2ZrCl2 (0.015 g) and H2BDC−NH2 (0.005
g) were dissolved in a mixture of 0.25 mL of DMA, 0.25 mL of CCl4,
and 8 drops of distilled water, and the mixture was then heated at 45
°C for 10 h. After the mixture slowly cooled down to room
temperature, yellow block crystals were obtained. IR (KBr pellet,
Figure 1. Assembly strategy of ZrT-2 and ZrMC-1-X (X = NO2, NH2). The coordination environment of Cp3Zr3 SBB in ZrT-2 (a) and ZrMC-1
(b).
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Figure 2. (a) Molecular structure of ZrMC-2. (b) Comparison of the coordination environment of Cp3Zr3 SBBs in ZrMC-2 (b, c). Color code: S,
yellow. H atoms are omitted for clarity.
cm−1): 3350, 1606, 1546, 1462, 1400, 1020, 817, 773, 713, 617, 478.
in the same coordination environment with three BTC linkers
Elemental analysis (%): calculated for ZrMC-1-NH2·12DMA·4CCl4·
with the same orientation (Figure 1a); whereas in ZrMC-1,
3H2O (Zr12C160N18O55H216Cl8): C, 37.9; H, 4.2; N, 4.9. Found: C,
two BDC ligands are in the same orientation, and the other is
37.32; H, 4.66; N, 4.51.
in the opposite orientation (Figure 1b). In other words, the
ZrMC-2. Excess Cp2ZrCl2 (0.015 g) and H2BDC−SO3Na (0.005 g)
carboxylate-bridged Cp3Zr3 SBBs in ZrT-2 are symmetric,
were dissolved in 1 mL of CH3CN and 3 drops of distilled water, and
while those in ZrMC-1 are asymmetric. This reveals that
symmetry breaking in carboxylate-bridged Cp3Zr3 SBB could
be an effective strategy to develop low-symmetric Zr-based
MCs.
the mixture was then heated at 65 °C for 10 h. After the mixture
slowly cooled down to room temperature, colorless block crystals
were obtained. IR (KBr pellet, cm−1): 3350, 1608, 1556, 1452, 1382,
1127, 1190, 1113, 1045, 1018, 997, 819, 771, 713, 623, 480. ZrMC-2·
CH3CN·NaCl·50H2O (Zr18C156NO130H206ClNaS8): C, 30.56; H,
3.38; N, 0.23. Found: C, 30.57; H, 3.42; N, <0.3.
ZrMC-3. Excess Cp2ZrCl2 (0.015 g) and thiophene-2,5-dicarboxylic
acid (0.005 g) were dissolved in 1 mL of MeOH and 3 drops of
distilled water, and the mixture was then heated at 45 °C for 10 h.
After the mixture slowly cooled down to room temperature, colorless
block crystals were obtained. IR (KBr pellet, cm−1): 3350, 1552, 1531,
1390, 1018, 817, 769, 684, 599, 515, 470. ZrMC-3·48H2O
(Zr18C144O108H222S9Cl6): C, 29.68; H, 3.84; N, 0. Found: C, 29.15;
H, 3.30; N, <0.3.
Deacetalization−Knoevenagel Condensation Reactions. The
catalytic reactions were performed with 1 mmol of each substrate in
CDCl3 (2 mL), and the catalyst (1.2 mmol %) was then added,
followed by continuous stirring at 50 °C for 48 h. To follow up the
tandem reaction process, 1H NMR spectroscopy was utilized, and the
yields were calculated by the integration of benzylic protons at the
end of the reaction.
To validate this strategy, H2BDC-NO2 and H2BDC-NH2
were used to replace the mBDC in ZrMC-1, which
unsurprisingly resulted in two new window-shaped Zr-based
MCs, denoted as ZrMC-1-NO2 and ZrMC-1-NH2, respec-
tively. Notably, these two substituents in the 5-position of the
isophthalic acid do not affect their main structures relative to
ZrMC-1 but influence window sizes, environments, and cavity
volumes. The introduction of substituent causes the four
benzene rings of the wall to turn inward, leading to a reduction
in window size. Specifically, the window size and cavity
volumes of ZrMC-1-NO2 and ZrMC-1-NH2 are reduced to
5.7 × 9.7 Å2 and 4.7 × 8.8 Å2, and 117.7 Å3 and 83.53 Å3,
respectively. Moreover, both electron-acceptor −NO2 and
electron-donor −NH2 groups located at the outer edge and
bottom of MCs may serve as additional binding sites to
substrates with different electrical properties.
In the course of continuous exploration, we further
introduced the H2BDC−SO3Na with sulfonate group in the
5-position of the isophthalic acid to determine how this group
affects the resulting structure. Unexpectedly, an unprecedented
bowel-like Zr-based MC with a formula of {[Cp3Zr3(μ3-O)(μ2-
OH)3]3(BDC−SO3)4}Cl·Na·nS, abbreviated as ZrMC-2, built
from three Cp3Zr3 SBBs and four BDC−SO3H linkers, has
been produced (Figure 2a). In the structure of ZrMC-2, three
BDC−SO3 ligands are connected with three Cp3Zr3 SBBs,
forming a triangular prism core. Interestingly, it has been found
that the other deprotonated BDC−SO3 ligand functions as a
tridentate ligand to occupy the remaining uncoordinated sites
of the three Cp3Zr3 SBBs. Since only one sulfonate on the
ligand is coordinated, there are two distinct Cp3Zr3 SBBs in
ZrMC-2. Specifically, two Cp3Zr3 SBBs in this structure are all
coordinated by three carboxylates (Figure 2c), while the
remaining one is coordinated by two carboxylates and one
sulfonate (Figure 2b). To our knowledge, this is the first
Cp3Zr3-based coordination compound in which sulfonate is
involved in coordination. This implies that new Cp3Zr3-based
coordination complexes can be built by using other heterotopic
ligands with both sulfonate and carboxylate sites, disulfonate,
3. RESULTS AND DISCUSSION
The reaction between Cp2ZrCl2 and H2BDC in a mixture of
DMF and H2O resulted in the isolation of colorless crystals
with a formula of {[Cp3Zr3(μ3-O)(μ2-OH)3]4(BDC)6}4Cl·nS
(ZrMC-1, S = guest solvent molecule). Single-crystal X-ray
diffraction analysis revealed that ZrMC-1 crystallizes in the
̅
space group P1, featuring a cationic window-shaped container
topology (Figure 1b), whose charge is balanced by four Cl−
counteranions. In this structure, four approximately vertical
benzene rings of the BDC act as the wall, and two benzene
rings function as the bottom of MC. The window size of
ZrMC-1 is about 9.3 × 9.9 Å2, and the optimized intrinsic void
diameter and void volume of this MC are 6.65 and 153.76 Å3,
respectively. Although both ZrMC-1 and the classical Zr-based
tetrahedron, ZrT-2, are composed of four trinuclear Cp3Zr3
SBBs and six ligands, their structures are completely different
(Figure 1). Notably, in response to using lower C2-symmetric
V-shaped BDC compared to C3-symmetric 1,3,5-benzene-
tricarboxylic acid (H3BTC), a reduction in the symmetry of
Cp3Zr3 SBBs was realized. After careful analysis and
comparison of these two structures, it was found that, in the
ZrT-2 structure, the neighboring Zr centers of Cp3Zr3 SBB are
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Figure 3. (a) Structure of ZrMC-3. (b, c) Coordination environment of Cp3Zr3 SBBs in this structure. H atoms are omitted for clarity.
or trisulfonate ligands. Compared with ZrMC-1, the
coordination of sulfonate forces the structure to become
more compact. The optimized intrinsic void diameter and void
volume of this MC is 5.11 and 69.7 Å3, respectively.
Regarding the diversity and adjustability of Cp3Zr3 SBB in
ZrMC-1 and ZrMC-2, H2TDB, another type of V-shaped
ligand but with a larger bend angle than that of isophthalate-
type, is used, affording an unexpected zigzag-shaped MC,
ZrMC-3, with a formula of {[Cp3Zr3(μ3-O)(μ2-
OH)3]6(TDB)9}·6Cl·nS (Figure 3a). This structure contains
two parallel bowl-like prisms, whose bottoms are linked by one
TDB ligand. It should be noted that each bowl-like prism is
interconnected by three Cp3Zr3 SBBs and three TDB linkers,
which are similar to ZrMC-2. However, the remaining Zr
coordination sites at the bottom of this prism are sealed by
three carboxylates from two different TDB ligands, which are
very different from those in ZrMC-2. With a closer look at the
structure of ZrMC-3, it was found that while all Cp3Zr3 SBBs
are coordinated by carboxylate groups from TDB ligands, they
can be divided into two different types based on their opening
difference, resulting from the difference in dihedral angles
between the TDB square and Zr3 triangle face. Specifically, the
dihedral angles in two Cp3Zr3 SBBs bridged by TDB ligands
are about 79.043°, 82.001°, and 53.068°, respectively (Figures
3c and S1a), while those in type II are 49.010°, 69.938°, and
67.261°, respectively (Figures 3b and S1b).
Unfortunately, the nitrogen gas uptakes for the ZrMC-1
series and ZrMC-3 are negligible. This might be ascribed to
the fact that they are hydrogen-bonded frameworks, which are
built from Cl− anions and μ2-OH groups of the cationic Zr-
based MCs. Such hydrogen bonding interaction is weak,
resulting in their framework collapse during activation as
determined by PXRD (Figures S2−S4). In contrast, ZrMC-2
maintains its framework intact after activation (Figure S3b),
showing better N2 adsorption performance and demonstrating
a fully reversible type I isotherm with a Brunauer−Emmett−
Teller (BET) surface area of 249 m2 g−1 (Figure 4). The
porosity and desirable aperture of ZrMC-2 encouraged us to
investigate its absorption capacities for other gas further. As
shown in Figures S5 and S6, they demonstrated that ZrMC-2
could adsorb significant amounts of CO2 (34.84 cm3 g−1 under
293 K), H2 (68.23 cm3 g−1 under 77 K), olefins (31.46 and
40.36 cm3 g−1 for C2H4 and C3H6 under 293 K, respectively),
and alkynes (45.70 and 58.90 cm3 g−1 for C2H2 and C3H4
under 293 K, respectively).
Figure 4. N2 adsorption at 77 K for ZrMC-2.
In recent years, there has been a growing interest in the
design and synthesis of bifunctional heterogeneous cascade
catalysts with both Lewis acid and basic sites to effectively
catalyze the tandem one-pot deacetalization−Knoevenagel
reaction, because of less waste, lower cost, and fewer
purification steps.38−42 Notably, the deacetalization−Knoeve-
nagel condensation reaction comprises two catalytic steps. In
the first step, deacetalization of dimethoxymethylbenzene is
carried out to generate benzaldehyde by acid sites, while, in the
second step, Knoevenagel reaction between benzaldehyde and
malononitrile is performed to obtain benzylidene malononitrile
by base sites. With these in mind, we believed that ZrMC-1-
NH2, combining acidic Zr4+ sites and basic −NH2 sites, could
be a suitable catalyst to the aforementioned reaction. In order
to prove this point, ZrMC-1 and ZrMC-1-NO2 were used to
explore their catalytic activity for tandem deacetalization−
Knoevenagel condensation reaction. As shown in Table 1, the
yield of the corresponding benzylidenemalononitrile product
catalyzed by ZrMC-1-NH2 reaches 93.2%. This finding is
much higher than yields of ZrMC-1 (21.3%) and ZrMC-1-
NO2 (25.4%) when benzaldehyde dimethyl acetal is utilized as
a substrate. Notably, this tandem catalytic performance based
on 1-(dimethoxymethyl)-4-methoxybenzene substrate dis-
played the same trend by the three MC catalysts described
above. These results highly demonstrate that the existence of
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Article
Authors
Table 1. Reaction of Deacetalization−Knoevenagel
Condensation
Shunfu Du − College of Chemistry, Fuzhou University, Fuzhou
350108, China; Key Laboratory of Optoelectronic Materials
Chemistry and Physics, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Science, Fuzhou
50002, China
Xuying Yu − College of Chemistry, Fuzhou University, Fuzhou
350108, China; Key Laboratory of Optoelectronic Materials
Chemistry and Physics, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Science, Fuzhou
50002, China
Reactant
R = H
Entry
Yield (%)
No catalyst
ZrMC-1
ZrMC-1-NO2
ZrMC-1-NH2
No catalyst
ZrMC-1
trace
21.9
25.4
93.2
trace
29.1
28.6
97.8
R = OCH3
ZrMC-1-NO2
ZrMC-1-NH2
Guoliang Liu − Key Laboratory of Optoelectronic Materials
Chemistry and Physics, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Science, Fuzhou
50002, China; orcid.org/0000-0001-7418-5659
Mi Zhou − Key Laboratory of Optoelectronic Materials
Chemistry and Physics, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Science, Fuzhou
50002, China; orcid.org/0000-0002-0752-1488
EI-Sayed M. El-Sayed − Key Laboratory of Optoelectronic
Materials Chemistry and Physics, Fujian Institute of Research
on the Structure of Matter, Chinese Academy of Science,
Fuzhou 50002, China; University of the Chinese Academy of
Sciences, Beijing, P. R. China; Chemical Refining Laboratory,
Refining Department, Egyptian Petroleum Research Institute,
Nasr City, Cairo, Egypt
Zhanfeng Ju − Key Laboratory of Optoelectronic Materials
Chemistry and Physics, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Science, Fuzhou
50002, China; orcid.org/0000-0002-5081-4032
Kongzhao Su − Key Laboratory of Optoelectronic Materials
Chemistry and Physics, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Science, Fuzhou
50002, China; orcid.org/0000-0001-9557-6982
both Lewis acid and base catalyst sites is necessary for the
promotion of the tandem deacetalization−Knoevenagel
condensation reaction.
4. CONCLUSIONS
In conclusion, we have constructed three types of Zr-based
MCs, including three window-shaped, bowel-like, and zigzag-
shaped structures, by using simple V-shaped dicarboxylic
ligands and Cp3Zr3 SBBs. Specifically, the window-shaped
ZrMC-1 provides an excellent platform for window environ-
ment modification in MCs by introducing functional groups
such as −NO2, −NH2, and so on. The respective MCs, based
on these groups, especially ZrMC-1-NH2, showed improved
performance in practical applications, such as a tandem
deacetalization−Knoevenagel condensation reaction. To the
best of our knowledge, bowel-like ZrMC-2 presents the first
Cp3Zr3-based coordination compound in which sulfonate is
involved in coordination. Moreover, the supramolecular
framework of ZrMC-2 is retained after vacuum activation
and can therefore adsorb considerable amounts of N2 as well as
other gases. ZrMC-3 has a rare zigzag-shaped structure, which
bridges two prism-shaped MCs parallel to each other through
TDB linkers. This example prefigures that Zr-based MCs could
be promising supramolecular building blocks to construct
hierarchical coordination nanostructures. All the aforemen-
tioned results indicate that Cp3Zr3 SBBs have great potential in
the construction of MCs.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.cgd.0c01561
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by the Nation-
al Key R&D Program of China (2017YFA0700102), the
Strategic Priority Research Program of the Chinese Academy
of Sciences (XDB20000000), the National Natural Science
Foundation of China (21707143, 51603206), and the Natural
Science Foundation of Fujian Province (2016J05056).
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REFERENCES
CCDC 2027347−2027351 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
■
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AUTHOR INFORMATION
Corresponding Author
■
Daqiang Yuan − Key Laboratory of Optoelectronic Materials
Chemistry and Physics, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Science, Fuzhou
50002, China; orcid.org/0000-0003-4627-072X;
Email: ydq@fjirsm.ac.cn
696
https://dx.doi.org/10.1021/acs.cgd.0c01561
Cryst. Growth Des. 2021, 21, 692−697

Crystal Growth & Design
pubs.acs.org/crystal
Article
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697
https://dx.doi.org/10.1021/acs.cgd.0c01561
Cryst. Growth Des. 2021, 21, 692−697