A Calix[4]resorcinarene-Based [Co12] Coordination Cage for Highly Efficient Cycloaddition of CO2 to Epoxides

Article abstract of DOI:10.1021/acs.inorgchem.9b02473

The design and synthesis of polynuclear metal cluster-based coordination cages is of considerable interest due to their appealing structural characteristics and potential applications. Herein, we report a calix[4]resorcinarene-based [Co12] coordination cage, [Co12(TPC4R-I)2(1,3-BDC)10(μ3-OH)4(H2O)10(DMF)2]·7DMF·23H2O (1), assembled with 2 bowl-shaped calix[4]resorcinarenes (TPC4R-I), 10 angular 1,3-benzenedicarboxylates (1,3-BDC), and 12 Co(II) cations. Remarkably, it is shown to be a highly efficient recyclable heterogeneous catalyst for CO2 conversion due to its exposed Co(II) Lewis acid sites.

Full text of DOI:10.1021/acs.inorgchem.9b02473

Article
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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
A Calix[4]resorcinarene-Based [Co12] Coordination Cage for Highly
Efficient Cycloaddition of CO2 to Epoxides
Ting-Ting Guo,†,§ Xiao-Fang Su,†,§ Xianxiu Xu,‡ Jin Yang,*,† Li-Kai Yan,† and Jian-Fang Ma*,†
†Key Lab for Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, China
‡College of Chemistry, Chemical Engineering and Materials Science, Key Laboratory of Molecular and Nano Probes, Ministry of
Education, Shandong Normal University, Jinan 250014, China
S
* Supporting Information
ABSTRACT: The design and synthesis of polynuclear metal cluster-based
coordination cages is of considerable interest due to their appealing
structural characteristics and potential applications. Herein, we report a
calix[4]resorcinarene-based [Co12] coordination cage, [Co12(TPC4R-
I)2(1,3-BDC)10(μ3-OH)4(H2O)10(DMF)2]·7DMF·23H2O (1), assembled
with 2 bowl-shaped calix[4]resorcinarenes (TPC4R-I), 10 angular 1,3-
benzenedicarboxylates (1,3-BDC), and 12 Co(II) cations. Remarkably, it is
shown to be a highly efficient recyclable heterogeneous catalyst for CO2
conversion due to its exposed Co(II) Lewis acid sites.
the assembly of calix[4]resorcinarene-based (TPC4R-I)
coordination cage. Herein, a remarkable [Co12] coordination
cage with [Co4O4] cubanes, namely, [Co12(TPC4R-I)2(1,3-
BDC)10(μ3-OH)4(H2O)10(DMF)2]·7DMF·23H2O (1), was
assembled with functionalized calix[4]resorcinarene (TPC4R-
I), angular 1,3-H2BDC, and Co(II) cations (Scheme 1).
Notably, 1 represents a unique example of [Co12] coordination
cages with [Co4O4] cubanes surrounded by calix[4]-
resorcinarenes. Importantly, 1 features highly efficient cyclo-
addition of CO2 with epoxides as a recyclable heterogeneous
catalyst.
INTRODUCTION
■
The design and assembly of polynuclear metal cluster-based
coordination cages have attracted great interest due to their
unique structures and broad applications including gas
sorption, drug delivery, and catalysis.1−11 Notably, organic
linkers with special structural features play a key role in
controlling structures of the polynuclear metal cluster-based
coordination cages.12−14 In this context, calix[4]arenes have
been widely used in coordination chemistry.15−21 Among
them, calix[4]resorcinarenes are exceedingly attractive supra-
molecules owing to their special structural features modified by
functionalized groups.22−27 As a result, the design and
assembly of the polynuclear metal cluster-based coordination
cages with calix[4]resorcinarenes are quite desirable yet remain
a synthetic challenge.28
Scheme 1. Construction of Calix[4]resorcinarene-Based
a
[Co12] Cage of 1
Carbon dioxide (CO2) is responsible for the increasing
global warming as well as exacerbating climate changes as a
major greenhouse gas.29 The chemical conversion of CO2 via
the catalytic reaction is an attractive method for the recycling
of carbons.30−32 In this regard, the CO2 cycloaddition to
epoxides has attracted considerable attention.33 To date,
numerous catalysts have been developed for the cycloaddition
of CO2 with epoxides.34−36 The polynuclear metal cluster-
based coordination cages with metal Lewis acid sites, as an
emerging type of heterogeneous catalysts, have received
increasing interest owing to their easy separation and reusage
in catalysis.36,37 However, nearly no polynuclear metal cluster-
based coordination cages with calix[4]resorcinarenes have
been applied as heterogeneous catalysts for the CO2
cycloaddition to epoxides thus far.37
a
The coordinated water and DMF molecules are not shown for
clarity.
Based on the considerations above, an appropriate angular
1,3-benzenedicarboxylic acid (1,3-H2BDC) was used to tune
Received: August 14, 2019
© XXXX American Chemical Society
A
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Based on our experiments and the cage structures, we can infer
that the substitutents (−SO3H and −OH vs −H) of the
isophthalate derivatives play a key role in the construction of
different cage motifs. In other words, the formation of the
[Co12] and [Co16] cages is highly dependent on the additional
negative charges of the isophthalate derivatives used.22
Cycloaddition of CO2 with Epoxides. Given the Co(II)
Lewis acid sites in 1, the CO2 cycloaddition to epoxide was
studied in detail.39−41 Prior to the catalytic study, 1 was
activated to remove the coordinated water and DMF
molecules.42,43 Typically, 1 was solvent-exchanged with dry
acetone for at least ten times over 3 days. Then, the sample was
filtered and activated at 80 °C under vacuum for more than 10
h. Initially, the cycloaddition between epichlorohydrin (ECH)
and CO2 was utilized as the model to scout for the optimum
reaction conditions (Scheme 2). After the catalytic reactions
RESULTS AND DISCUSSION
■
Crystal Structure of 1. The formula of 1 is established by
X-ray diffraction analysis, thermogravimetric analysis, as well as
elemental analysis. Crystallographic diffraction demonstrates
that 1 features an unusual calix[4]resorcinarene-based [Co12]
coordination cage assembled with two independent [Co4O4]
cubanes and four independent mononuclear Co(II) cations
(Figure 1). Two pairs of centrosymmetrically related [Co4O4]
Scheme 2. Schematic Drawing for Cycloaddition of CO2
with ECH
finished, the reaction flask was immediately placed in cold
water. Then, the residue was washed with cold CH2Cl2 (3 mL)
and centrifugated to isolate the products. The reaction
products were then purified by extraction with a mixture of
CH2Cl2 and water (8 mL, 1/1 v/v). The product carbonates
were characterized by 1H NMR (Figures S2−S10). The
corresponding conversions were determined by gas chroma-
tography (GC) (Figures S11 and S12). As listed in Table S2,
the CO2 cycloaddition with ECH by 1 (0.002 mmol) gave only
25% conversion after 6 h in the absence of tetra-n-
butylammonium bromide (n-Bu4NBr). Accordingly, a con-
version of ca. 47% was achieved with only n-Bu4NBr as catalyst
under the same reaction condition (entry 2, Table S2).
Notably, when n-Bu4NBr and 1 were applied as cocatalysts, the
conversion of ECH was significantly enhanced to 96% (entry
4, Table S2). Moreover, the conversion of ECH was
investigated with different amounts of 1 under the same
condition. When the amount of 1 reached 0.003 mmol, the
conversion was enhanced to 98% after 6 h (entries 3−5, Table
S2). Further, under elevated reaction temperatures from 30 to
60 °C, the corresponding conversions of ECH increased from
30% to the final 96% after 6 h (entries 4 and 6−8, Table S2).
Noticeably, compared to the activated sample of 1, the
unactivated one gave the relatively low conversion (entry 9,
Table S2). As a result, subsequent studies on cycloadditions of
CO2 with epoxides were carried out with n-Bu4NBr (0.25
mmol) and the activated sample of 1 (0.002 mmol) at 60 °C
and 1 atm CO2 for 6 h.
Figure 1. Crystal structure of [Co12] coordination cage of 1.
cubanes and four mononuclear Co(II) cations are bridged by
the 1,3-BDC anions to produce the remarkable [Co12]
coordination cage, which is further ligated by two TPC4R-I
species on both sides (Figure 1). The [Co4O4] cubane consists
of four Co(II) cations, two u2-O atoms, and two u3-O atoms
(Figure S1a). Each Co(II) cation in the [Co4O4] cubane is
linked by the u2-O and u3-O atoms. Notably, two 2-(pyrazol-3-
yl)pyridine groups from two different TPC4R-I species chelate
two Co(II) cations of one [Co4O4] cubane, thus highly
stabilizing the [Co4O4] cubane. The Co−O distances in the
[Co4O4] cubane range from 2.006(4) to 2.325(4) Å, and the
Co···Co separations by the oxygen atoms vary from 3.09 to
3.66 Å. To our knowledge, 1 represents a unique example of
[Co12] coordination cages with [Co4O4] cubanes surrounded
by calix[4]resorcinarenes. Bond valence sum (BVS) calcu-
lations indicate that the cobalt atoms are in +2 oxidation state
(Table S1). After removal of solvents, the free void volume in
each unit cell is about 39.7% according to calculation with
PLATON.38
Notably, we recently reported two related [Co16] cages,
[Co16(TPC4R-I)2(HL)4(L)8(H2O)24]·12DMF·4H2O (1-
SO3H) and [Co16(TPC4R-I)2(HL1)4(L1)8(H2O)16]·
17DMA·H2O (1-OH) (H3L = 5-sulfonic-isophthalic acid,
H3L1 = 5-hydroxy-isophthalic acid, and DMA = N,N′-
dimethylacetamide).22 Each [Co16] cage consists of 16 Co(II)
cations, 2 calix[4]resorcinarenes, and 12 angular isophthalate
derivatives. Obviously, the two types of [Co12] and [Co16]
cages were prepared from the analogous precursors under
similar reaction conditions (e.g., reaction temperatures and
solvents), but their cage structures are completely different.
To explore the applicability of the catalytic reactions, the
epoxides with different structures were studied as sub-
strates.44−48 The cycloaddition of CO2 with ECH, 1,4-
bis(oxiran-2-ylmethoxy)butane (BOMB), 2-((benzyloxy)-
methyl)oxirane (BMO), 2-(phenoxymethyl)oxirane (PMO),
and 2-(butoxymethyl)oxirane (2-BMO) (entries 1−5, Table 1)
afford the high conversions of 96%, 96%, 86%, 86%, and 81%,
respectively, within 6 h. In contrast, when the electron-donors
B
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Table 1. Cycloaddition of CO2 with Different Epoxides by
a
1
a
Reaction conditions: 1 (0.002 mmol), n-Bu4NBr (0.25 mmol),
epoxide (5 mmol), CO2 (1 atm), and 60 °C.
1,4-di(oxiran-2-yl)butane (DOB), 2-butyloxirane (2-BO), and
2-phenyloxirane (2-PO) were utilized as substrates, the
corresponding conversions were reduced (entries 6−8, Table
1). However, only 61% of the overall 2-(((2-ethylhexyl)oxy)-
methyl)oxirane (EOMO) was converted into the product
under the same condition (entry 9, Table 1), which can be
attributed to the high steric hindrance of substrate.49−51
Further, when the reaction time reached 12 h, most of the
substrates were completely converted into the catalytic
products (entries 1−7, Table 1). In contrast, the conversions
of the electron-donor 2-PO and the steric hindrance EOMO
were only 82% and 83%, respectively, after 12 h (entries 8 and
9). Noticeably, within 12 h, the epoxide was converted into the
single cyclic carbonate with >99% selectivity determined by 1H
NMR data (Table S3).52
Moreover, catalytic kinetics for the cycloaddition of PMO
with CO2 was also studied with 1 and n-Bu4NBr as cocatalysts.
The catalytic experiment was conducted at different reaction
time intervals. With the increasing reaction time, the
conversions of the substrate PMO were gradually enhanced,
as depicted in Figure 2a. After 6 h, ca. 86% of PMO was
converted into the target product, and the final conversion
reached 97% after 8 h.
Notably, 1 can be recovered from the reaction system by
centrifugation, washed with acetone, and dried under vacuum
at 50 °C before the next catalytic cycle. As illustrated in Figure
2b, 1 still retains the high catalytic performance after five runs,
demonstrating its good reusability during the CO2 cyclo-
addition with epoxides. In addition, the heterogeneity was also
studied for the catalytic reaction. 1 was removed after 4 h of
the catalytic reaction. As depicted in Figure 2a, no obvious
increase was observed for the catalytic product in the filtrate,
suggesting the heterogeneity of the catalysis. The PXRD
Figure 2. (a) Catalytic dynamic study for the cycloaddition of CO2
with PMO catalyzed by 1 (blue) and filtrate (green). (b) Recyclable
cycloaddition of CO2 with PMO using 1 as catalyst.
pattern of 1 after the cycloaddition reaction was determined
and demonstrated its structural integrity after catalysis (Figure
S13a). Overall, the high catalytic activity and easy reusability
made 1 an excellent catalyst for CO2 cycloaddition to epoxides.
Additionally, 1 features the high catalytic efficiency for the
cycloaddition of CO2 under relatively mild conditions. The
catalytic activities of 1 toward the CO2 cycloaddition reactions
are comparable to the known metal organic compounds (Table
S4). For example, for the reaction time of 6 h, the conversion
of ECH for 1 is 96% at 60 °C and 1 atm CO2, while the
corresponding conversion for catalyst [Zr6 (μ3 -
OH)8(OH)8(Cu-L2)4] (L2 = 6,13-dicarboxy-1,4,8,11-tetraa-
zacyclotetradecane) (a) reached 94% at increased temperature
(90 °C) and gas pressure (10 atm) (Table S4).53 For PMO,
the 64% conversion was achieved with 1 as catalyst at 60 °C
for 4 h, whereas the conversion is only 41% for catalyst
{[Mn5(L3)(H2O)6(DMA)2]·5DMA·4C2H5OH} (L3 =
5,10,15,20-tetra(4-(3,5-dicarboxylphenoxy)phenyl)porphyrin)
(b) at 80 °C for 4 h.49 Notably, the substrate PMO was
completely converted with 1 as catalyst at 60 °C for 12 h.
Nevertheless, the similar conversions of PMO were acquired
when the reaction temperatures were elevated to 80 and 100
°C for {[(CH3)2NH2]6[Cd3(L4)(H2O)2]·12H2O} (L4 =
C
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resorcin[4]arene-functionalized dodecacarboxylate) (c) and
[Ni2(L5)(DMF)(H2O)4] (L5 = tetrakis(4-carboxyphenyl)-
ethylene) (d), respectively (Table S4).37,42 These results
demonstrate that the catalytic performance of 1 is comparable
to those of the metal organic compounds determined at high
reaction temperatures and elevated gas pressures.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b02473.
■
S
Experimental section, rystallographic data, 1H NMR
spectra, tables of data, and GC spectra (PDF)
Moreover, the catalytic activity of 1 for the CO2 cyclo-
addition is comparable to the related mononuclear, dinuclear,
or tetranuclear metal cation-based complexes (Table S5). For
instance, an 82% conversion of 2-PO was acquired using 1 as
catalyst at 60 °C for 12 h, while the similar conversion was
achieved even at increased reaction temperature (100 °C) for
monuclear Co(II)-based {[{Co(L6)(L7)(2H2O)}·2H2O]n}
(L6 = trans,trans-muconate dianion and L7 1,2-bis(4-pyridyl)-
ethane) (e).54 Particularlly, the same conversion was obtained
for dinuclear Co(II)-based {[Co6(L8)4(L9)3(H2O)3]·12DMF·
9H2O}n (f) (L8 = 4,4′,4″-s-triazine-1,3,5-triyl-tri-p-amino-
benzate and L9 = 1,4-diazabicyclo[2.2.2]octane), when the
reaction temperature was elevated to 80 °C and the reaction
time was prolonged to 15 h (Table S5).55 Noticeably, the final
conversion of 2-PO is only 68% for tetranuclear Ni(II)-based
{[Ni4(L10)(μ3-OH)2(H2O)6]·2H2O·DMA}n (L10 = 5,5′,5″-
(methylsilanetriyl)triisophthalate) (g) at increased reaction
temperature (100 °C) and gas pressure (10 atm).56
It is well-established that the metal cation Lewis acids could
act as the catalytic active sites for the CO2 cycloaddition
reactions.57−62 The coordinated water molecules and solvents
in the single Co(II) cation and the [Co4O4] unit were removed
by fully activating the sample of 1 before the catalytic study.
Thereby, the single Co(II) cation and the [Co4O4] unit in 1
feature the exposed Lewis acid sites and act as the catalytic
centers, which resulted in a synergistic effect for the
cycloaddition reaction of CO2.
To further explore the role of the whole cage structure in the
CO2 cycloaddition reaction, the reference experiment for the
cycloaddition of ECH and CO2 was conducted using cobalt
acetate (0.002 mmol) and n-Bu4NBr (0.25 mmol) under the
same condition.54 A total conversion of 67% was obtained with
cobalt acetate and n-Bu4NBr as cocatalysts at 60 °C for 6 h
(Table S2). Obviously, this conversion is much lower than that
(96%) with 1 and n-Bu4NBr as cocatalysts. The result suggests
that the whole cage structure with rich Lewis acid Co(II) sites
is effective for improving the CO2 cycloaddition to epoxides. In
addition, the ICP analysis of the filtrate after the cycloaddition
of CO2 ruled out the leaching of the Co(II) cations from 1,
confirming the whole cage as the catalyst.
Accession Codes
CCDC 1941476 contains the supplementary crystallographic
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 Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
■
*E-mail: yangj808@nenu.edu.cn. (J.Y.)
*E-mail: majf247@nenu.edu.cn. Fax: +86-431-85098620. (J.-
F.M.)
ORCID
Li-Kai Yan: 0000-0002-1352-4095
Jian-Fang Ma: 0000-0002-4059-8348
Author Contributions
§T.-T.G. and X.-F.S. contributed equally to this manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (21771034 and 21471029).
■
REFERENCES
■
(1) 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.
(2) Brown, C. J.; Toste, F. D.; Bergman, R. G.; Raymond, K. N.
Supramolecular Catalysis in Metal−Ligand Cluster Hosts. Chem. Rev.
2015, 115, 3012−3035.
(3) Zhang, G.; Mastalerz, M. Organic Cage Compounds−from
Shape-Persistency to Function. Chem. Soc. Rev. 2014, 43, 1934−1947.
(4) Geng, D.; Han, X.; Bi, Y.; Qin, Y.; Li, Q.; Huang, L.; Zhou, K.;
Song, L.; Zheng, Z. Merohedral Icosahedral M48 (M = CoII, NiII)
Cage Clusters Supported by Thiacalix[4]arene. Chem. Sci. 2018, 9,
8535−8541.
(5) Bi, Y.; Du, S.; Liao, W. Thiacalixarene-Based Nanoscale
Polyhedral Coordination Cages. Coord. Chem. Rev. 2014, 276, 61−72.
(6) Jin, P.; Dalgarno, S. J.; Atwood, J. L. Mixed Metal-Organic
Nanocapsules. Coord. Chem. Rev. 2010, 254, 1760−1768.
(7) Dalton, D. M.; Ellis, S. R.; Nichols, E. M.; Mathies, R. A.; Toste,
CONCLUSIONS
■
In summary, we present a calix[4]resorcinarene-based [Co12]
coordination cage 1, constructed by 2 bowl-shaped calix[4]-
resorcinarenes, 10 angular 1,3-benzenedicarboxylates, and 12
Co(II) cations. 1 represents an unusual example of [Co12]
coordination cages with [Co4O4] cubanes surrounded by
calix[4]resorcinarenes. Importantly, the activated sample of 1
with exposed Lewis acidic sites, as a recyclable catalyst, features
high catalytic activities for CO2 cycloaddition to epoxides. This
work offers a feasible route for the design and synthesis of
functional polynuclear metal cluster-based coordination cages.
Further efforts to assemble the calix[4]resorcinarene-based
cages featuring elegant motifs and potential applications are
ongoing in our lab.
12−
F. D.; Bergman, R. G.; Raymond, K. N. Supramolecular Ga4L6
Cage Photosensitizes 1,3-Rearrangement of Encapsulated Guest via
Photoinduced Electron Transfer. J. Am. Chem. Soc. 2015, 137,
10128−10131.
(8) Mondal, B.; Mukherjee, P. S. Cage Encapsulated Gold
Nanoparticles as Heterogeneous Photocatalyst for Facile and Selective
Reduction of Nitroarenes to Azo Compounds. J. Am. Chem. Soc. 2018,
140, 12592−12601.
(9) Liu, M.; Liao, W.; Hu, C.; Du, S.; Zhang, H. Calixarene-Based
Nanoscale Coordination Cages. Angew. Chem., Int. Ed. 2012, 51,
1585−1588.
(10) Wang, S.; Sawada, T.; Ohara, K.; Yamaguchi, K.; Fujita, M.
Capsule−Capsule Conversion by Guest Encapsulation. Angew. Chem.,
Int. Ed. 2016, 55, 2063−2066.
D
DOI: 10.1021/acs.inorgchem.9b02473
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(11) Rizzuto, F. J.; Ramsay, W. J.; Nitschke, J. R. Otherwise
Unstable Structures Self-Assemble in the Cavities of Cuboctahedral
Coordination Cages. J. Am. Chem. Soc. 2018, 140, 11502−11509.
(12) Rathnayake, A. S.; Fraser, H. W. L.; Brechin, E. K.; Dalgarno, S.
J.; Baumeister, J. E.; Rungthanaphatsophon, P.; Walensky, J. R.;
Barnes, C. L.; Atwood, J. L. Oxidation State Distributions Provide
Insight into Parameters Directing the Assembly of Metal−Organic
Nanocapsules. J. Am. Chem. Soc. 2018, 140, 13022−13027.
(13) Mastalerz, M. Shape-Persistent Organic Cage Compounds by
Dynamic Covalent Bond Formation. Angew. Chem., Int. Ed. 2010, 49,
5042−5053.
structed by a New Resorcin[4]arene-Based Tetracarboxylate. Inorg.
Chem. 2015, 54, 1744−1755.
(28) Pei, W.-Y.; Xu, G. H.; Yang, J.; Wu, H.; Chen, B. L.; Zhou, W.;
Ma, J.-F. Versatile Assembly of Metal-Coordinated Calix[4]-
resorcinarene Cavitands and Cages through Ancillary Linker Tuning.
J. Am. Chem. Soc. 2017, 139, 7648−7656.
(29) Tu, W.; Zhou, Y.; Zou, Z. Photocatalytic Conversion of CO2
into Renewable Hydrocarbon Fuels: State-of-the-Art Accomplish-
ment, Challenges, and Prospects. Adv. Mater. 2014, 26, 4607−4626.
(30) Fu, Y.; Sun, D.; Chen, Y.; Huang, R.; Ding, Z.; Fu, X.; Li, Z. An
Amine-Functionalized Titanium Metal−Organic Framework Photo-
catalyst with Visible-Light-Induced Activity for CO2 Reduction.
Angew. Chem., Int. Ed. 2012, 51, 3364−3367.
(31) Huff, C. A.; Sanford, M. S. Cascade Catalysis for the
Homogeneous Hydrogenation of CO2 to Methanol. J. Am. Chem.
Soc. 2011, 133, 18122−18125.
(32) Chen, L.; Yu, F.; Shen, X.; Duan, C. N-CND Modified NH2-
UiO-66 for Photocatalytic CO2 Conversion under Visible Light by a
Photo-Induced Electron Transfer Process. Chem. Commun. 2019, 55,
4845−4848.
(33) Yang, Q.; Yang, C.-C.; Lin, C.-H.; Jiang, H.-L. Metal−Organic-
Framework-Derived Hollow N-Doped Porous Carbon with Ultrahigh
Concentrations of Single Zn Atoms for Efficient Carbon Dioxide
Conversion. Angew. Chem., Int. Ed. 2019, 58, 3511−3515.
(34) Bobbink, F. D.; Vasilyev, D.; Hulla, M.; Chamam, S.; Menoud,
F.; Laurenczy, G.; Katsyuba, S.; Dyson, P. J. Intricacies of Cation−
Anion Combinations in Imidazolium Salt Catalyzed Cycloaddition of
CO2 Into Epoxides. ACS Catal. 2018, 8, 2589−2594.
(35) Li, P.-Z.; Wang, X.-J.; Liu, J.; Lim, J. S.; Zou, R.; Zhao, Y. A
Triazole-Containing Metal−Organic Framework as a Highly Effective
and Substrate Size-Dependent Catalyst for CO2 Conversion. J. Am.
Chem. Soc. 2016, 138, 2142−2145.
(36) Dong, J.; Cui, P.; Shi, P.-F.; Cheng, P.; Zhao, B. Ultrastrong
Alkali-Resisting Lanthanide-Zeolites Assembled by [Ln60] Nanocages.
J. Am. Chem. Soc. 2015, 137, 15988−15991.
(14) Acharyya, K.; Mukherjee, P. S. Organic Imine Cages: Molecular
Marriage and Applications. Angew. Chem., Int. Ed. 2019, 58, 8640−
8653.
(15) Joseph, R.; Rao, C. P. Ion and Molecular Recognition by Lower
Rim 1,3-Di-conjugates of Calix[4]arene as Receptors. Chem. Rev.
2011, 111, 4658−4702.
(16) Mattiuzzi, A.; Jabin, I.; Mangeney, C.; Roux, C.; Reinaud, O.;
Santos, L.; Bergamini, J.-F.; Hapiot, P.; Lagrost, C. Electrografting of
Calix[4]arenediazonium Salts to Form Versatile Robust Platforms for
Spatially Controlled Surface Functionalization. Nat. Commun. 2012,
3, 1130.
(17) Wang, S.; Gao, X.; Hang, X.; Zhu, X.; Han, H.; Li, X.; Liao, W.;
Chen, W. Calixarene-Based {Ni18} Coordination Wheel: Highly
Efficient Electrocatalyst for the Glucose Oxidation and Template for
the Homogenous Cluster Fabrication. J. Am. Chem. Soc. 2018, 140,
6271−6277.
(18) Wang, S.; Gao, X.; Hang, X.; Zhu, X.; Han, H.; Liao, W.; Chen,
W. Ultrafine Pt Nanoclusters Confined in a Calixarene-Based {Ni24}
Coordination Cage for High-Efficient Hydrogen Evolution Reaction.
J. Am. Chem. Soc. 2016, 138, 16236−16239.
(19) Adhikari, L.; Larm, N. E.; Wagle, D. V.; Atwood, J. L.; Baker, G.
A. Facile, One-Pot, in Aqua Synthesis of Catalytically Competent
Gold Nanoparticles Using Pyrogallol[4]arene as The Sole Reagent.
Chem. Commun. 2019, 55, 6261−6264.
(37) Lu, B.-B.; Jiang, W.; Yang, J.; Liu, Y.-Y.; Ma, J.-F.
Resorcin[4]arene-Based Microporous Metal−Organic Framework as
an Efficient Catalyst for CO2 Cycloaddition with Epoxides and Highly
Selective Luminescent Sensing of Cr2O72−. ACS Appl. Mater. Interfaces
2017, 9, 39441−39449.
(38) Spek, A. L. PLATON SQUEEZE: A Tool for the Calculation of
the Disordered Solvent Contribution to the Calculated Structure
Factors. Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 9−18.
(39) Li, X.-Y.; Ma, L.-N.; Liu, Y.; Hou, L.; Wang, Y.-Y.; Zhu, Z.
Honeycomb Metal-Organic Framework with Lewis Acidic and Basic
Bifunctional Sites: Selective Adsorption and CO2 Catalytic Fixation.
ACS Appl. Mater. Interfaces 2018, 10, 10965−10973.
(40) Gao, W.-Y.; Chen, Y.; Niu, Y.; Williams, K.; Cash, L.; Perez, P.
J.; Wojtas, L.; Cai, J.; Chen, Y.-S.; Ma, S. Crystal Engineering of an
nbo Topology Metal−Organic Framework for Chemical Fixation of
CO2 under Ambient Conditions. Angew. Chem., Int. Ed. 2014, 53,
2615−2619.
(41) Huang, X.; Chen, Y.; Lin, Z.; Ren, X.; Song, Y.; Xu, Z.; Dong,
X.; Li, X.; Hu, C.; Wang, B. Zn-BTC MOFs with Active Metal Sites
Synthesized via a Structure-Directing Approach for Highly Efficient
Carbon Conversion. Chem. Commun. 2014, 50, 2624−2627.
(42) Zhou, Z.; He, C.; Xiu, J.; Yang, L.; Duan, C. Metal−Organic
Polymers Containing Discrete Single-Walled Nanotube as a
Heterogeneous Catalyst for the Cycloaddition of Carbon Dioxide to
Epoxides. J. Am. Chem. Soc. 2015, 137, 15066−15069.
(20) Ling, I.; Kumari, H.; Mirzamani, M.; Sobolev, A. N.; Garvey, C.
J.; Atwood, J. L.; Raston, C. L. Phase Dependent Structural
Perturbation of a Robust Multicomponent Assembled Icosahedral
Array. Chem. Commun. 2018, 54, 10824−10827.
(21) Fang, Y.; Xiao, Z.; Li, J.; Lollar, C.; Liu, L.; Lian, X.; Yuan, S.;
Banerjee, S.; Zhang, P.; Zhou, H.-C. Formation of a Highly Reactive
Cobalt Nanocluster Crystal within a Highly Negatively Charged
Porous Coordination Cage. Angew. Chem., Int. Ed. 2018, 57, 5283−
5287.
(22) Guo, T.-T.; Cheng, D.-M.; Yang, J.; Xu, X.; Ma, J.-F.
Calix[4]resorcinarene-Based [Co16] Coordination Cages Mediated
by Isomorphous Auxiliary Ligands for Enhanced Proton Conduction.
Chem. Commun. 2019, 55, 6277−6280.
(23) Kobayashi, K.; Yamanaka, M. Self-Assembled Capsules Based
on Tetrafunctionalized Calix[4]resorcinarene Cavitands. Chem. Soc.
Rev. 2015, 44, 449−466.
(24) Kane, C. M.; Banisafar, A.; Dougherty, T. P.; Barbour, L. J.;
Holman, K. T. Enclathration and Confinement of Small Gases by the
Intrinsically 0D Porous Molecular Solid, Me,H,SiMe2. J. Am. Chem.
Soc. 2016, 138, 4377−4392.
(25) Han, X.; Xu, Y.-X.; Yang, J.; Xu, X.; Li, C.-P.; Ma, J.-F. Metal-
Assembled, Resorcin[4]arene-Based Molecular Trimer for Efficient
Removal of Toxic Dichromate Pollutants and Knoevenagel Con-
densation Reaction. ACS Appl. Mater. Interfaces 2019, 11, 15591−
15597.
(26) Lu, B.-B.; Yang, J.; Che, G.-B.; Pei, W.-Y.; Ma, J.-F. Highly
Stable Copper(I)-Based Metal−Organic Framework Assembled with
Resorcin[4]arene and Polyoxometalate for Efficient Heterogeneous
Catalysis of Azide−Alkyne “Click” Reaction. ACS Appl. Mater.
Interfaces 2018, 10, 2628−2636.
(27) Lv, L.-L.; Yang, J.; Zhang, H.-M.; Liu, Y.-Y.; Ma, J.-F. Metal-Ion
Exchange, Small-Molecule Sensing, Selective Dye Adsorption, and
Reversible Iodine Uptake of Three Coordination Polymers Con-
(43) Ng, C. K.; Toh, R. W.; Lin, T. T.; Luo, H.-K.; Hor, T. S. A.;
Wu, J. Metal−Salen Molecular Cages as Efficient and Recyclable
Heterogeneous Catalysts for Cycloaddition of CO2 with Epoxides
under Ambient Conditions. Chem. Sci. 2019, 10, 1549−1554.
(44) Meng, X.; Ju, Z.; Zhang, S.; Liang, X.; von Solms, N.; Zhang,
X.; Zhang, X. Efficient Transformation of CO2 to Cyclic Carbonates
Using Bifunctional Protic Ionic Liquids under Mild Conditions. Green
Chem. 2019, 21, 3456−3463.
E
DOI: 10.1021/acs.inorgchem.9b02473
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(45) Sun, X.; Gu, J.; Yuan, Y.; Yu, C.; Li, J.; Shan, H.; Li, G.; Liu, Y.
A Stable Mesoporous Zr-Based Metal Organic Framework for Highly
Efficient CO2 Conversion. Inorg. Chem. 2019, 58, 7480−7487.
(46) Rachuri, Y.; Kurisingal, J. F.; Chitumalla, R. K.; Vuppala, S.; Gu,
Y.; Jang, J.; Choe, Y.; Suresh, E.; Park, D.-W. Adenine-Based Zn(II)/
Cd(II) Metal-Organic Frameworks as Efficient Heterogeneous
Catalysts for Facile CO2 Fixation into Cyclic Carbonates: A DFT-
Supported Study of the Reaction Mechanism. Inorg. Chem. 2019, 58,
11389−11403.
(61) Yang, Y.; Gao, C.-Y.; Tian, H.-R.; Min, J.; Ai, X.; Sun, Z.-M. A
Highly Stable MnII Phosphonate as a Highly Efficient Catalyst for
CO2 Fixation under Ambient Conditions. Chem. Commun. 2018, 54,
1758−1761.
(62) Zou, R.; Li, P. Z.; Zeng, Y. F.; Liu, J.; Zhao, R.; Duan, H.; Luo,
Z.; Wang, J. G.; Zou, R.; Zhao, Y. Bimetallic Metal-Organic
Frameworks: Probing the Lewis Acid Site for CO2 Conversion.
Small 2016, 12, 2334−2343.
(47) Wei, L.-Q.; Ye, B.-H. Efficient Conversion of CO2 via Grafting
Urea Group into a [Cu2(COO)4]-Based Metal−Organic Framework
with Hierarchical Porosity. Inorg. Chem. 2019, 58, 4385−4393.
(48) Wang, Y.; Li, S.; Yang, Y.; Shen, X.; Liu, H.; Han, B. A fully
Heterogeneous Catalyst Br-LDH for The Cycloaddition Reactions of
CO2 with Epoxides. Chem. Commun. 2019, 55, 6942−6945.
(49) Jiang, W.; Yang, J.; Liu, Y.-Y.; Song, S.-Y.; Ma, J.-F. A
Porphyrin-Based Porous rtl Metal−Organic Framework as an Efficient
Catalyst for the Cycloaddition of CO2 to Epoxides. Chem. - Eur. J.
2016, 22, 16991−16997.
(50) Wang, X.; Gao, W.-Y.; Niu, Z.; Wojtas, L.; Perman, J. A.; Chen,
Y.-S.; Li, Z.; Aguila, B.; Ma, S. A Metal−Metalloporphyrin Framework
Based on an Octatopic Porphyrin Ligand for Chemical Fixation of
CO2 with Aziridines. Chem. Commun. 2018, 54, 1170−1173.
(51) Lu, B.-B.; Yang, J.; Liu, Y.-Y.; Ma, J.-F. A Polyoxovanadate−
Resorcin[4]arene-Based Porous Metal−Organic Framework as an
Efficient Multifunctional Catalyst for the Cycloaddition of CO2 with
Epoxides and the Selective Oxidation of Sulfides. Inorg. Chem. 2017,
56, 11710−11720.
(52) Wang, X.; Zhou, Y.; Guo, Z.; Chen, G.; Li, J.; Shi, Y.; Liu, Y.;
Wang, J. Heterogeneous Conversion of CO2 into Cyclic Carbonates
at Ambient Pressure Catalyzed by Ionothermal-Derived Meso-
Macroporous Hierarchical Poly(ionic liquid)s. Chem. Sci. 2015, 6,
6916−6924.
(53) Zhu, J.; Usov, P. M.; Xu, W.; Celis-Salazar, P. J.; Lin, S.;
Kessinger, M. C.; Landaverde-Alvarado, C.; Cai, M.; May, A. M.;
Slebodnick, C.; Zhu, D.; Senanayake, S. D.; Morris, A. J. A New Class
of Metal-Cyclam-Based Zirconium Metal−Organic Frameworks for
CO2 Adsorption and Chemical Fixation. J. Am. Chem. Soc. 2018, 140,
993−1003.
(54) Ugale, B.; Dhankhar, S. S.; Nagaraja, C. M. Interpenetrated
Metal−Organic Frameworks of Cobalt(II): Structural Diversity,
Selective Capture, and Conversion of CO2. Cryst. Growth Des.
2017, 17, 3295−3305.
(55) Ugale, B.; Kumar, S.; Dhilip Kumar, T. J.; Nagaraja, C. M.
Environmentally Friendly, Co-catalyst-Free Chemical Fixation of CO2
at Mild Conditions Using Dual-Walled Nitrogen-Rich ThreeDimen-
sional Porous Metal-Organic Frameworks. Inorg. Chem. 2019, 58,
3925−3936.
(56) Gao, C.-Y.; Yang, Y.; Liu, J.; Sun, Z.-M. A NiII-Cluster-Based
MOF as an Efficient Heterogeneous Catalyst for the Chemical
Transformation of CO2. Dalton Trans. 2019, 48, 1246−1250.
(57) Gupta, M.; De, D.; Tomar, K.; Bharadwaj, P. K. From Zn(II)-
Carboxylate to Double-Walled Zn(II)-Carboxylato Phosphate MOF:
Change in the Framework Topology, Capture and Conversion of
CO2, and Catalysis of Strecker Reaction. Inorg. Chem. 2017, 56,
14605−14611.
(58) Puthiaraj, P.; Ravi, S.; Yu, K.; Ahn, W.-S. CO2 Adsorption and
Conversion into Cyclic Carbonates over a Porous ZnBr2-Grafted N-
Heterocyclic Carbene-Based Aromatic Polymer. Appl. Catal., B 2019,
251, 195−205.
(59) Zhou, Z.; He, C.; Yang, L.; Wang, Y. F.; Liu, T.; Duan, C. Y.
Alkyne Activation by a Porous Silver Coordination Polymer for
Heterogeneous Catalysis of Carbon Dioxide Cycloaddition. ACS
Catal. 2017, 7, 2248−2256.
(60) Bondarenko, G. N.; Dvurechenskaya, E. G.; Ganina, O. G.;
Alonso, F.; Beletskaya, I. P. Solvent-Free Synthesis of Cyclic
Carbonates from CO2 and Epoxides Catalyzed by Reusable
Alumina-Supported Zinc Dichloride. Appl. Catal., B 2019, 254,
380−390.
F
DOI: 10.1021/acs.inorgchem.9b02473
Inorg. Chem. XXXX, XXX, XXX−XXX