Fast and Robust Synthesis of Metalated PCN-222 and Their Catalytic Performance in Cycloaddition Reactions with CO2

Article abstract of DOI:10.1021/acs.organomet.9b00273

A simple and quick setup for the synthesis of PCN-222 and of a variety of metalated PCN-222(Co, Ni, Cu, and Zn), using of a microwave reactor, is reported for CO₂ fixation. Metalation of prophyrins by microwave heating has been evaluated throug

Full text of DOI:10.1021/acs.organomet.9b00273

Article
pubs.acs.org/Organometallics
Cite This: Organometallics XXXX, XXX, XXX−XXX
Fast and Robust Synthesis of Metalated PCN-222 and Their Catalytic
Performance in Cycloaddition Reactions with CO2
‡
Sergio Carrasco,‡ Amparo Sanz-Marco, and Belen Martín-Matute*
́
Department of Organic Chemistry, Stockholm University, Stockholm 10691, Sweden
S
* Supporting Information
ABSTRACT: A simple and quick setup for the synthesis of
PCN-222 and of a variety of metalated PCN-222(Co, Ni, Cu,
and Zn), using of a microwave reactor, is reported for CO2
fixation. Metalation of prophyrins by microwave heating has
been evaluated through UV−vis titration. PCN-222(M) were
obtained in a three-step, one-pot reaction in a remarkable 72%
yield in only 30 min. The materials have been characterized
using a variety of techniques. A study of CO2 fixation through
cycloaddition with epoxides and azidirines using metalated
PCNs as catalysts is described. Cyclic carbonates and
oxazolidinones were formed using CO2 at atmospheric
pressure under mild conditions. Higher activity was observed
when PCN-222(Co) was used compared to that with PCN-
222(Ni, Cu, Zn).
cocatalysts.15 Recently, the use of bifunctional porphyrins as
INTRODUCTION
■
catalysts where the cocatalyst is already incorporated into the
structure of the porphyrin has also been reported.16−19 In
general, high temperatures and/or high pressures of CO2 are
required when metallopophyrins are used.
The development of methods for the fixation of carbon dioxide
(CO2) would allow this abundant gas to be used as a one-
carbon building block for synthesis. This should be seen as a
very important goal as part of a move toward the sustainable
production of chemicals. CO2 has a high thermodynamic
stability, so it needs to be activated if it is to be used as a
feedstock for the synthesis of added-value organic com-
pounds.1 Both homogeneous and heterogeneous catalytic
approaches to this activation have been investigated.2−4 For
example, different porous materials have been synthesized and
used as heterogeneous catalysts, including metal−organic
frameworks (MOFs).5 MOFs are porous crystalline materials
that are obtained by the polymerization of organic linkers and
metal ions/clusters. Adsorption capacity for CO2, catalytic
efficiency for CO2 conversion, and recyclability are the three
key aspects to be considered when selecting a MOF for this
goal.
The cycloaddition reaction of CO2 with epoxides to give
cyclic carbonates6,7 is a remarkable reaction that leads to the
formation of important building blocks and proceeds with a
high atom economy (Scheme 1, top left). Different organo-
catalysts8−11 as well as metal catalysts2,12 have been used to
catalyze this reaction under homogeneous conditions. High
catalytic activity was observed when metalloporphyrins were
used as catalysts. These materials show high thermal stability
and straightforward formation by metal complexation, and they
have been prepared with a variety of structures bearing
different functional groups.13,14 Metalloporphyrins containing
metals such as Mg, Al, Cr, Cu, and Co have been tested as
Lewis acid catalysts, using, for example, ammonium salts as
Turning to heterogeneous catalysts20−25 based on porphyr-
ins, Zhou’s group have synthesized a series of new materials,
namely, PCN-224 (no metal, Ni, Co, Fe), using a linker-
elimination strategy.26 These MOFs consist of 3D nano-
channels formed by Zr6 clusters and metalloporphyrins. This
group pioneered the use of the porphyrinic zirconium MOF,
PCN-224(Co), as a catalyst for the cycloaddition reactions of
propylene oxide. Recently, new porphyrinic MOFs such as
CuE1,27 ZnTPy-BIM4/CNTs-3,28 MMPF-18,29 and CuN-
bOF5(TPyPNi)30 have been synthesized and successfully used
as catalysts in the cycloaddition reactions of epoxides. The use
of azidirines instead of epoxides as substrates for cycloaddition
reactions with CO2 yields oxazolidinones, which are also
important structures in pharmaceutical chemistry.31,32 One
example of a cycloaddition reaction with an azidirine was
reported using the porphyrinic Cu-containing MMPF-10 as the
catalyst.33 The products were obtained in high yields, although
a high pressure of CO2 (2 MPa) was used.
For all these reactions, the catalytic activity was found to be
similar to or higher than their homogeneous counterparts, but
the use of such heterogeneous catalysts also has significant
Special Issue: Organometallic Chemistry within Metal-Organic
Frameworks
Received: April 26, 2019
© XXXX American Chemical Society
A
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a
Scheme 1. Cycloaddition Reaction of CO2, TCPP(M), and PCN-222(Co) Channels
a
Top, left: Cycloaddition reaction of CO2 with epoxides and aziridines. Top, right: Schematic representation of TCPP(M). Bottom: Two
projections of PCN-222(Co) channels along different axes.
Scheme 2. Three-Step, One-Pot Synthesis of PCN-222 and PCN-222(Co, Ni, Cu or Zn)
advantages, such as simple catalyst separation and potential
catalyst reuse. When it comes to the PCN family, their Lewis
acidic character resulting from the presence of Zr metal ions as
well as the metalloporphyrins within the polymeric matrix
make them potential catalysts for the cycloaddition reactions of
CO2. The PCN-222(M) family (M = metal) are ideal
candidates, due to their extraordinarily large channels of 37
Å in diameter, larger than those of PCN-224, PCN-223, and
MOF-525.34,35 Large channels and pores facilitate substrate−
catalyst interactions and increase the catalytic efficiency. A
major drawback when it comes to the use of metalated PCN-
222(M) is that tedious synthetic procedures are needed.
Several steps are required to prepare the metalated porphyrins,
and then the framework itself also needs to be synthesized and
purified.36−38 If these materials are to be used in the
development of new catalytic applications,39 then the long
synthetic route is a significant disadvantage. It is essential to
have a fast and reliable procedure that can be used to prepare a
range of materials that will allow the identification of the one
with the highest catalytic activity. Our group has extensive
experience in the synthesis of diverse materials and its
application in catalysis.40−43
catalytic performance in the cycloaddition reactions of CO2
with epoxides and azidirines under atmospheric pressure is also
described.
RESULTS
■
We developed a three-step, one-pot microwave-assisted
synthesis of PCN-222 and PCN-222(Co, Ni, Cu or Zn) as
shown in Scheme 2. The first step (Scheme 2, top) involves
the formation of the Zr preclusters through the reaction of
ZrOCl2 with 2-fluorobenzoic acid (2FBA) (5 min, 140 °C, 70
W, 0 bar, in N,N-dimethylformamide (DMF)). Metalation of
tetrakis(4-carboxyphenyl)porphyrin [TCPP(H2)] was carried
out in step 2 (Scheme 2, bottom), and TCPP(M) was
obtained in only 5 min at 175 °C in DMF under microwave
irradiation (85 W, 1 bar). We found that a ratio of MCl2 to
TCPP(H2) of 5:1 (mol/mol) was needed for this reaction. For
the preparation of nonmetalated PCN-222, step 2 was also
carried out but in the absence of metal salts. The purpose of
this was to solubilize the TCPP(H2). In the last step of the
synthesis (step 3), the two mixtures from steps 1 and 2 were
combined and treated with trifluoroacetic acid (TFA; 20 min,
150 °C, 35 W, 1 bar). Steps 2 and 3 are discussed thoroughly
in the following sections. Further information on the
development of this procedure is found in the Supporting
Information.
In this paper, we describe a new, efficient, and general
method for the synthesis of a range of metalated PCN-222
structures in one pot. The protocol allows a variety of these
materials to be obtained in a simple and fast manner. Their
B
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Figure 1. UV−vis spectra of TCPP(H2) (left) and TCPP(Co) (right), before (1) and after (2) adding an excess of HCl. Conditions: (1) 6.32 μM
TCPP(H2/Co) in DMF; (2) 3.61 μM TCPP(H2/Co) + 8.6 mM HCl in DMF, resulting in TCPP(H4)2+ and unaltered TCPP(Co).
Evaluation of the Metalation Efficiency. The metalation
procedure described above (Scheme 2, step 2) was carried out
under microwave conditions for 5 min at 175 °C. As our
approach is based on the direct mixing of as-synthesized
metalated TCPP(M) with Zr preclusters, we avoid the tedious
and time-consuming purification process required to isolate the
starting material. This metalation procedure is significantly
simpler than those reported in the literature for the synthesis of
metalated porphyrins with −COOH moieties.26 The efficiency
of the metalation procedure was evaluated through UV−vis
titration of the reaction mixtures formed in step 2 (i.e., without
any purification or isolation). The optical properties of
metalated porphyrins and porphyrin derivatives are very well
known.44,45 It is known that TCPP(H2) shows two different
absorption bands in DMF as a consequence of π → π*
transitions (metal-to-linker or linker-to-metal charge transfer),
one centered at 422 nm corresponding to the Soret (B) band
and four Q bands at 515, 550, 590, and 646 nm (see Table
S1).46 We used the new Q-band arising at 666 nm in the fully
protonated TCPP(H4)2+ for quantification purposes (Figure 1,
left), as metalated TCPP(M) species prepared with an excess
of metal salt (5:1) do not show this band in the red region of
the spectra (Figure 1, right).
By plotting the absorbance value of the band at 666 nm for
nonmetalated TCPP(H2) while adding increasing amounts of
HCl (see Figure S2), it is possible to relate the degree of
protonation of the porphyrin to a maximum value correspond-
ing to the titration end point (TCPP(H4)2+). When the
porphyrin is fully metalated (TCPP(M)), no changes in
absorbance at this wavelength should be observed, and it
should not be possible to plot a titration curve (see Figure S3).
Thus, the difference in absorbance between TCPP(H4)2+ and
TCPP(M) at 666 nm can be used to measure the efficiency of
the metalation.
elemental analysis (see the Supporting Information). DMF
plays a crucial role in the metalation procedure; it helps the
metal to enter the ring after deprotonation of the
porphyrin.4748 Titration curves can therefore be used to
estimate the amount of Co in the system as an alternative to
elemental analysis. It may be possible to extend this approach
to other systems.
Optimization of the Synthesis. The influence of the
reaction conditions on the outcome of the PCN-222 synthesis
step was evaluated (i.e., the effects on the crystalline structure
and the final yield of the reaction temperature (150 and 175
°C), reaction time (10 and 20 min), and the molar ratio
modulator: Zr4+(5, 10, 25 and 50)). Benzoic acid, which is
typically used as the modulator for the synthesis of PCN-222,
was replaced here by 2-fluorobenzoic acid (2FBA, see the
Supporting Information) (Scheme 2, step 1). The use of a
modulator as well as the molar ratio modulator/Zr4+ were
crucial; importantly, the amount of PCN-222 obtained
decreased when increased amounts of 2FBA were used,
irrespective of the other reaction parameters (see Table S3).
We hypothesize that the presence of 2FBA decreases the
solubility of Zr preclusters in the reaction medium;49 this
would allow less modulator to be used than in syntheses where
benzoic acid was used. In general, neither reaction temperature
nor reaction time had any dramatic effect on the final yield
(see Table S3). We then checked the crystallinity of all the
materials synthesized. The highest purity phase was obtained
when a ratio of Zr4+ to 2FBA of 1:25 was used at 150 °C for 20
min (see Figure S5 and Table S3). Further optimization
allowed us to decrease the amount of 2FBA to a ratio of 1:15
(Zr4+/2FBA) without losing crystallinity. Thus, we selected
150 °C, 20 min, and a 2FBA/Zr4+ ratio of 1:15 as the optimal
conditions. Under these conditions, PCN-222 was obtained in
70% yield (on a scale giving ca. 100 mg). The same conditions
were used for the synthesis of PCN-222(Cu, Zn, Co, Ni).
PXRD confirmed that the materials formed showed the same
pure crystalline phase (Figure 2), which can be attributed to
the use of MW heating.50 It is important to mention that the
excess of the metal M present in the reaction mixture (TCPP/
We tested our hypothesis by evaluating the efficiency of the
metalation reaction to form TCPP(Co) using different ratios
of TCPP/CoCl2 (see Figure S3). A 1:5 excess of CoCl2 is
needed to ensure metalation of all the porphyrins in the MOF
formed during step 3 (Figure 1, Table S2), as confirmed by
C
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Cu, or Zn) was evaluated in the cycloaddition reactions of
epoxides and azidirines with carbon dioxide. The cycloaddition
reaction of 1,2-epoxydecane (1a) with CO2 (1 atm) using
tetrabutylammonium bromide (TBAB) as cocatalyst (6 mol
%) at rt was investigated first (Scheme 3a). PCN-222(Co)
a
Scheme 3. Kinetic Profiles of Cycloaddition of 1a and 1c
Figure 2. PXRD patterns of PCN-222 and PCN-222(M) compared
to the theoretical pattern (in black, CCDC 893545).
MCl2 = 1:5) during the porphyrin metalation step did not
interfere with the structural ion/ion clusters. DMF has a dual
role in this reaction: It acts as a solvent, but also at the
temperatures used, DMF decomposes to form dimethylamine,
which is basic enough to deprotonate both the pyrroles and the
carboxylic acid moieties, enabling the metalation and polymer-
ization reactions, respectively.51
Finally, we optimized the washing procedure (Figure S7).
Remarkably, only one washing step using DMF/HCl (0.5 M
aqueous) was required to remove the excess of 2FBA, as
confirmed by 1H NMR spectroscopy (Figure S8). Four
additional washing steps using EtOH were required to remove
traces of HCl within the MOF pores. Further details about the
washing procedure and the characterization of the materials
prepared in this work can be found in the Supporting
Information, including thermogravimetric analysis (Figure S9),
nitrogen sorption isotherms (Figures S10 and S11), scanning
electron microscopy (Figures S12 and S13), carbon dioxide
sorption isotherms (Figure S15), elemental analysis (Table
S6), and ultraviolet−visible (UV−vis, Figure S16) and infrared
spectroscopies (Figure S17).
a
(a) Kinetic profile of cycloaddition of 1a (0.2 mmol) catalyzed by
different PCN-222(M). (b) Kinetic profile of cycloaddition of 1c (0.2
mmol) catalyzed by PCN-222(Co). Yield was determined using an
internal standard.
Table S4 summarizes the main procedures used to prepare
all the PCN-222 and PCN-222(M) structures. This simple
protocol works well, so the tedious metalation procedures
reported in the literature for the preparation of PCN-222(M)
MOFs, which generally involve protection of the −COOH
moieties of the TCPP, long metalation steps under harsh
conditions, and then deprotection. The method presented here
(Scheme 2) substantially decreases the overall time needed
from typically 2 days to 30 min; it also uses low amounts of
modulators and yields up to 100 mg of PCN-222 or PCN-
222(M) per batch.
The reproducibility and robustness of the procedure was
evaluated by synthesizing 10 batches of PCN-222(Co). These
materials all gave similar diffraction patterns (see Figure S6)
and were formed in yields of (71.6 1.3)% on a scale of 100
mg/batch. Thus, this procedure affords significantly increased
overall yields in a short synthesis time frame.49
showed higher activity than PCN-222(Cu, Ni, Zn), and 2a was
obtained in 73% yield. A shorter reaction time was required for
the cycloaddition reaction of 1,2-epoxypentane (1c) with CO2
catalyzed by PCN-222(Co), and a quantitative yield was
obtained after 12 h (Scheme 3b). This behavior may be
attributed to the easier diffusion of smaller substrates into the
channels of the porous material.29,30 Pore size distribution (12
and 31 Å, inset Figure S10), BET surface area (2016 m2/g,
Figure S11), and affinity toward CO2 (−17.6 kJ/mol as heat of
adsorption, Figure S15) were in agreement with those values
previously reported. Nonmetalated PCN-222 was also tested in
the cycloaddition reactions of 1a and 1c, but lower activity was
observed. This suggests that the presence of a metalated
porphyrin that can act as a Lewis acid catalyst is important for
the cycloaddition reaction (Table 1, entries 2 and 6). Also,
lower activity was observed when a homogeneous analog
(TCPP(Co)) was used as catalyst (entries 3 and 7). The
difference in activity between the homogeneous and
heterogeneous catalysts was greater for epoxide 1c than for
1a (32 vs 16%). This result is consistent with the idea that
smaller substrates (i.e., 1c) can access the catalytic centers
inside the MOF more easily. Using TBAB or CoCl2 in the
absence of the catalyst resulted in negligible yields (entries 4, 8,
and 9).
It must be mentioned that this procedure cannot be
extended to the synthesis of TCPP(Fe), probably as a
consequence of the ability of Fe2+ cations to interact with
the −COO− groups of the linker. Cross-linked two-dimen-
sional polymeric Fe-TCPP structures have been reported
elsewhere.52
Cycloaddition of Epoxides and Azidirines with CO2.
The catalytic activity of PCN-222 and PCN-222(M = Co, Ni,
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a
temperatures and shorter times than epoxides with longer
carbon chains, even though their electronic properties were
similar (i.e., 1b−d vs 1a). Additionally, halogenated sub-
stituted epoxides (1e,f), styrene (1g), and 2-(phenoxymethyl)-
oxirane (1h) gave cyclic carbonates in excellent yields. The
efficiency of PCN-222(Co) in the fixation of CO2 was further
tested by reaction with aziridines to give oxazolidinones. Under
mild conditions, a variety of azidirines were tested, and the
corresponding oxazolidinones 4a−e were obtained in good
yields.
The recyclability of the catalyst is an important subject in
heterogeneous catalysis. The catalytic activity toward 1c
remains constant after 4 runs (ca. 95% yield after 24 h, Figure
3). Furthermore, to prove the catalytic perfomance of the
material, the yield of 2c is checked at shorter times (12 h)
showing ca. 40% yield in consecutive runs (Figure S18),
confirming a similar reaction rate for different runs. Both the
crystallinity and morphology were maintained (Figures S19
and S20). Using scanning electron microscopy, we demon-
strated that after 4 catalytic runs, the hexagonal rods were
unaltered. The sizes of the crystals decreased slightly from 1.3
to 0.9 μm, and the edges became rounded, but the aspect ratio
remained similar (3.5).53
Table 1. Control Experiments
b
entry
epoxide
catalyst
time (h)
yield (%)
1
2
3
4
5
6
7
8
9
1a
1a
1a
1a
1c
1c
1c
1c
1c
PCN-222(Co)
PCN
TCPP(Co)
27
27
27
27
12
12
12
12
12
73
58
57
<5
99
67
67
<5
41
PCN-222(Co)
PCN
TCPP(Co)
CoCl2
a
Reaction conditions: epoxide 1 (0.2 mmol), CO2 (1 atm), catalyst (1
mol % based on Co), TBAB (6 mol %), no solvent, room
temperature. Yield determined by H NMR spectroscopy using an
internal standard.
b
1
The scope of the reaction was then studied (Scheme 4).
Epoxide substrates bearing alkyl chains of different lengths
were tested, and the corresponding products were obtained in
excellent yields (2a−d). Smaller epoxides required lower
PCN-222(Co) showed a high catalytic activity in the
cycloaddition reactions, and a wide range of products were
obtained under milder conditions compared to other
a
Scheme 4. Reaction Scope
a
Conditions: substrate 1 or 3 (0.2 mmol), CO2 (1 atm), catalyst (1 mol % based on Co), TBAB (6 mol %), and no solvent. Yield determined by
b
1H NMR spectroscopy using an internal standard, isolated yields in parentheses. Ratio of regioisomers.
E
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ACKNOWLEDGMENTS
■
This project was supported by the Swedish Research Council
̊
through Vetenskapsradet and Formas, the Knut and Alice
̈
Wallenberg Foundation (KAW 2016.0072), the Goran
Gustafsson Foundation, and NordForsk through NordCO2.
REFERENCES
■
(1) Liu, Q.; Wu, L.; Jackstell, R.; Beller, M. Using carbon dioxide as
a building block in organic synthesis. Nat. Commun. 2015, 6, 5933.
(2) Cokoja, M.; Bruckmeier, C.; Rieger, B.; Herrmann, W. A.; Kuhn,
̈
F. E. Transformation of Carbon Dioxide with Homogeneous
Transition-Metal Catalysts: A Molecular Solution to a Global
Challenge? Angew. Chem., Int. Ed. 2011, 50, 8510−8537.
(3) Lu, X.-B.; Ren, W.-M.; Wu, G.-P. CO2 Copolymers from
Epoxides: Catalyst Activity, Product Selectivity, and Stereochemistry
Control. Acc. Chem. Res. 2012, 45, 1721−1735.
Figure 3. Study of recyclability. Conditions: epoxide 1c (2 mmol),
CO2 (1 atm), catalyst (1 mol % based on Co), TBAB (6 mol %), no
1
solvent, room temperature for 24 h. Yield determined by H NMR
spectroscopy using an internal standard.
(4) James, B. R.; Boissonnault, J. A.; Wong-Foy, A. G.; Matzger, A.
J.; Sanford, M. S. Structure activity relationships in metal−organic
framework catalysts for the continuous flow synthesis of propylene
carbonate from CO2 and propylene oxide. RSC Adv. 2018, 8, 2132−
2137.
porphyrin-based catalysts (see Table S9). Furthermore, the
recyclability study demonstrates the efficiency and robustness
of the material.
(5) Maina, J. W.; Pozo-Gonzalo, C.; Kong, L.; Schutz, J.; Hill, M.;
̈
́
Dumee, L. F. Metal organic framework based catalysts for CO2
conversion. Mater. Horiz. 2017, 4, 345−361.
CONCLUSIONS
(6) Shaikh, A.-A. G.; Sivaram, S. Organic Carbonates. Chem. Rev.
1996, 96, 951−976.
■
We have described a new microwave-assisted synthesis of
metalated PCN-222. By optimizing different synthetic
parameters such as reaction time, reaction temperature, and
the amount of modulator, we were able to obtain PCN-222 as
a pure crystalline phase in excellent yields and in very short
reaction times. The simple and straightforward procedure for
the synthesis of metalated PCN-222(M = Co, Ni, Cu, and Zn)
avoids tedious protection/deprotection steps of the carboxylic
acid functional groups of TCPP. A new in situ UV−vis
titration procedure was established for the quantification of the
metalation efficiency. A general washing/activation procedure
was also developed, yielding 100 mg of PCN-222(M) per
batch. The catalytic activity of PCN-222(Co) was demon-
strated in the cycloaddition of epoxides and azidirines with
CO2 under remarkably mild reaction conditions under CO2 at
atmospheric pressure. Furthermore, the material can be
recycled for up to 4 runs, maintaining its catalytic activity
and crystallinity.
̈
̈
̈
(7) Schaffner, B.; Schaffner, F.; Verevkin, S. P.; Borner, A. Organic
Carbonates as Solvents in Synthesis and Catalysis. Chem. Rev. 2010,
110, 4554−4581.
(8) Liu, N.; Xie, Y.-F.; Wang, C.; Li, S.-J.; Wei, D.; Li, M.; Dai, B.
Cooperative Multifunctional Organocatalysts for Ambient Conversion
of Carbon Dioxide into Cyclic Carbonates. ACS Catal. 2018, 8,
9945−9957.
(9) Wang, J.; Zhang, Y. Boronic Acids as Hydrogen Bond Donor
Catalysts for Efficient Conversion of CO2 into Organic Carbonate in
Water. ACS Catal. 2016, 6, 4871−4876.
(10) Zhou, H.; Wang, G.-X.; Zhang, W.-Z.; Lu, X.-B. CO2 Adducts
of Phosphorus Ylides: Highly Active Organocatalysts for Carbon
Dioxide Transformation. ACS Catal. 2015, 5, 6773−6779.
(11) Hong, M.; Kim, Y.; Kim, H.; Cho, H. J.; Baik, M.-H.; Kim, Y.
Scorpionate Catalysts for Coupling CO2 and Epoxides to Cyclic
Carbonates: A Rational Design Approach for Organocatalysts. J. Org.
Chem. 2018, 83, 9370−9380.
(12) Chen, J.-H.; Deng, C.-H.; Fang, S.; Ma, J.-G.; Cheng, P.
Binuclear molybdenum alkoxide as the versatile catalyst for the
conversion of carbon dioxide. Green Chem. 2018, 20, 989−996.
(13) Callot, H. J. Ring expansions and contractions of metal-
loporphyrins. Dalton Trans. 2008, 6346−6357.
ASSOCIATED CONTENT
* Supporting Information
■
S
(14) Barona-Castano, J. C.; Carmona-Vargas, C. C.; Brocksom, T. J.;
̃
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.9b00273.
de Oliveira, K. T. Porphyrins as Catalysts in Scalable Organic
Reactions. Molecules 2016, 21, 310−337.
(15) North, M.; Pasquale, R.; Young, C. Synthesis of cyclic
carbonates from epoxides and CO2. Green Chem. 2010, 12, 1514−
1539.
Experimental details, characterization data, and NMR
spectra (PDF)
(16) Ema, T.; Miyazaki, Y.; Shimonishi, J.; Maeda, C.; Hasegawa, J.
Bifunctional Porphyrin Catalysts for the Synthesis of Cyclic
Carbonates from Epoxides and CO2: Structural Optimization and
Mechanistic Study. J. Am. Chem. Soc. 2014, 136, 15270−15279.
(17) Jiang, X.; Gou, F.; Chen, F.; Jing, H. Cycloaddition of epoxides
and CO2 catalyzed by bisimidazole-functionalized porphyrin cobalt-
(III) complexes. Green Chem. 2016, 18, 3567−3576.
(18) Maeda, C.; Shimonishi, J.; Miyazaki, R.; Hasegawa, J.-Y.; Ema,
T. Highly Active and Robust Metalloporphyrin Catalysts for the
Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and
Carbon Dioxide. Chem. - Eur. J. 2016, 22, 6556−6563.
(19) Maeda, C.; Sasaki, S.; Ema, T. Electronic Tuning of Zinc
Porphyrin Catalysts for the Conversion of Epoxides and Carbon
Dioxide into Cyclic Carbonates. ChemCatChem 2017, 9, 946−949.
AUTHOR INFORMATION
Corresponding Author
*E-mail: belen.martin.matute@su.se.
ORCID
■
Sergio Carrasco: 0000-0003-0024-1392
́
Belen Martín-Matute: 0000-0002-7898-317X
Author Contributions
‡S.C. and A.S.-M. contributed equally to this work.
Notes
The authors declare no competing financial interest.
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(20) Ding, M.; Flaig, R. W.; Jiang, H.-L.; Yaghi, O. M. Carbon
capture and conversion using metal− organic frameworks and MOF-
based materials. Chem. Soc. Rev. 2019, 48, 2783−2828.
(21) Yang, Q.; Yang, C.-C.; Lin, C.-H.; Jiang, H.-L. Metal−Organic-
Framework-Derived Hollow N-Doped PorousCarbon with Ultrahigh
Concentrations of Single Zn Atoms for Efficient Carbon Dioxide
Conversion. Angew. Chem., Int. Ed. 2019, 58, 3511−3515.
(22) Ding, M.; Jiang, H.-L. Incorporation of Imidazolium-Based
Poly(ionic liquid)s into a Metal−Organic Framework for CO2
Capture and Conversion. ACS Catal. 2018, 8, 3194−3201.
(23) Ding, M.; Chen, S.; Liu, X.-Q.; Sun, L.-B.; Lu, J.; Jiang, H.-L.
Metal−Organic Framework-Templated Catalyst: Synergyin Multiple
Sites for Catalytic CO2 Fixation. ChemSusChem 2017, 10, 1898−
1903.
(24) Hou, S.-L.; Dong, J.; Jiang, X.-L.; Jiao, Z.-H.; Zhao, B. A Noble-
Metal-Free Metal−Organic Framework (MOF) Catalyst for the
Highly Efficient Conversion of CO2 with Propargylic Alcohols. Angew.
Chem., Int. Ed. 2019, 58, 577−581.
(25) Xu, H.; Cao, C.-S.; Hu, H.-S.; Wang, S.-B.; Liu, J.-C.; Cheng,
P.; Kaltsoyannis, N.; Li, J.; Zhao, B. High Uptakeof ReO4@ and CO2
Conversion by a Radiation-Resistant Thorium−Nickle [Th48Ni6]
Nanocage-Based Metal−OrganicFramework. Angew. Chem., Int. Ed.
2019, 58, 6022−6027.
(26) Feng, D.; Chung, W.-C.; Wei, Z.; Gu, Z.-Y.; Jiang, H.-L.; Chen,
Y.-P.; Darensbourg, D. J.; Zhou, H.-C. Construction of Ultrastable
Porphyrin Zr Metal−Organic Frameworks through Linker Elimi-
nation. J. Am. Chem. Soc. 2013, 135, 17105−17110.
(27) Dutta, G.; Jana, A. K.; Natarajan, S. Chemical Fixation of CO2
and Other Heterogeneous Catalytic Studies by Employing a Layered
Cu-Porphyrin Prepared Through Single-Crystal to Single-Crystal
Exchange of a Zn Analogue. Chem. - Asian J. 2018, 13, 66−72.
(28) Jayakumar, S.; Li, H.; Chen, J.; Yang, Q. Cationic Zn−
Porphyrin Polymer Coated onto CNTs as a Cooperative Catalyst for
the Synthesis of Cyclic Carbonates. ACS Appl. Mater. Interfaces 2018,
10, 2546−2555.
Chemical Warfare Agent Simulants. ACS Nano 2015, 9, 12358−
12364.
́
(39) Pascanu, V.; Gonzalez Miera, G.; Inge, A. K.; Martín-Matute, B.
Metal-Organic Frameworks as Catalysts for Organic Synthesis: A
Critical Perspective. J. Am. Chem. Soc. 2019, 141, 7223−7234.
(40) Valiente, A.; Carrasco, S.; Sanz-Marco, A.; Tai, C.-W.; Bermejo
́
Gomez, A.; Martín-Matute, B. Aerobic Homocoupling of Arylboronic
Acids Catalyzed by Regenerable Pd(II)@MIL-88B-NH2(Cr). Chem-
CatChem 2019, DOI: 10.1002/cctc.201900556.
(41) Yuan, N.; Pascanu, V.; Huang, Z.; Valiente, A.; Heidenreich,
N.; Leubner, S.; Inge, A. K.; Gaar, J.; Stock, N.; Persson, I.; Martín-
Matute, B.; Zou, X. Probing the Evolution of Palladium Species in
Pd@MOF Catalysts during the Heck Coupling Reaction: An
Operando X-ray Absorption Spectroscopy Study. J. Am. Chem. Soc.
2018, 140, 8206−8217.
(42) Pascanu, V.; Carson, F.; Solano, M. V.; Su, J.; Zou, X.;
Johansson, M. J.; Martín-Matute, B. Selective Heterogeneous C−H
Activation/Halogenation Reactions Catalyzed by Pd@MOF Nano-
composites. Chem. - Eur. J. 2016, 22, 3729−3737.
́
(43) Pascanu, V.; Bermejo Gomez, A.; Ayats, C.; Platero-Prats, A.;
̀
Carson, F.; Su, J.; Yao, Q.; Pericas, M.; Zou, X.; Martín-Matute, B. A
Double−Supported Silica − Metal-Organic Framework Palladium
Nanocatalyst for Aerobic Oxidation of Alcohols under Batch and
Continuous Flow Regimes. ACS Catal. 2015, 5, 472−479.
(44) Senge, M. O.; Fazekas, M.; Notaras, E. G. A.; Blau, W. J.;
Zawadzka, M.; Locos, O. B.; Ni Mhuircheartaigh, E. M. Nonlinear
Optical Properties of Porphyrins. Adv. Mater. 2007, 19, 2737−2774.
(45) Zheng, W.; Shan, N.; Yu, L.; Wang, X. UV−visible, fluorescence
and EPR properties of porphyrins and metalloporphyrins. Dyes Pigm.
2008, 77, 153−157.
(46) Jeong, E.-Y.; Burri, A.; Lee, S.-Y.; Park, S.-E. Synthesis and
catalytic behavior of tetrakis(4-carboxyphenyl) porphyrin-periodic
mesoporous organosilica. J. Mater. Chem. 2010, 20, 10869−10875.
(47) Adler, A. D.; Longo, F. R.; Kampas, F.; Kim, J. On the
preparation of metalloporphyrins. J. Inorg. Nucl. Chem. 1970, 32,
2443−2445.
(48) Bommer, J. C.; Hambright, P. Heme, Chlorophyll, and Bilins:
Methods and Protocols; Springer Science & Business Media: Totowa,
NJ, 2008; p 61.
(49) Liu, C.-M.; Zhang, D.-Q.; Hao, X.; Zhu, D.-B. A Chinese Pane-
Like 2D Metal-Organic Framework Showing Magnetic Relaxation and
Luminescence Dual-Functions. Sci. Rep. 2017, 7, 11156.
(50) Klinowski, J.; Almeida Paz, F. A.; Silva, P.; Rocha, J.
Microwave-Assisted Synthesis of Metal−Organic Frameworks. Dalton
Trans. 2011, 40, 321−330.
(29) Gao, W.-Y.; Tsai, C.-Y.; Wojtas, L.; Thiounn, T.; Lin, C.-C.;
Ma, S. Interpenetrating Metal−Metalloporphyrin Framework for
Selective CO2 Uptake and Chemical Transformation of CO2. Inorg.
Chem. 2016, 55, 7291−7294.
(30) He, L.; Nath, J. K.; Lin, Q. Robust multivariate metal−
porphyrin frameworks for efficient ambient fixation of CO2 to cyclic
carbonates. Chem. Commun. 2019, 55, 412−415.
(31) Bozdogan, B.; Appelbaum, P. C. Oxazolidinones: activity, mode
of action, and mechanism of resistance. Int. J. Antimicrob. Agents 2004,
23, 113−119.
(51) Zhang, J.; White, G. B.; Ryan, M. D.; Hunt, A. J.; Katz, M. J.
Dihydrolevoglucosenone (Cyrene) As a Green Alternative to N,N-
Dimethylformamide (DMF) in MOF Synthesis. ACS Sustainable
Chem. Eng. 2016, 4, 7186−7192.
(32) Diekema, D. J.; Jones, R. N. Oxazolidinones. Drugs 2000, 59,
7−16.
(33) 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.
(34) Epp, K.; Semrau, A. L.; Cokoja, M.; Fischer, R. A. Dual Site
Lewis-Acid Metal-Organic Framework Catalysts for CO2 Fixation:
Counteracting Effects of Node Connectivity, Defects and Linker
Metalation. ChemCatChem 2018, 10, 3506−3512.
́
(52) Fidalgo-Marijuan, A.; Barandika, G.; Bazan, B.; Urtiaga, M.-K.;
Arriortua, M.-I. Self-assembly of iron TCPP (meso-tetra(4-
carboxyphenyl)porphyrin) into a chiral 2D coordination polymer.
Polyhedron 2011, 30, 2711−2716.
(53) Meng, A.-N.; Chaihu, L.-X.; Chen, H.-H.; Gu, Z.-Y. Ultrahigh
Adsorption and Singlet-Oxygen Mediated Degradation for Efficient
Synergetic Removal of Bisphenol A by a Stable Zirconium-Porphyrin
Metal-Organic Framework. Sci. Rep. 2017, 7, 6297.
(35) Shaikh, S. M.; Usov, P. M.; Zhu, J.; Cai, M.; Alatis, J.; Morris, A.
J. Synthesis and Defect Characterization of Phase-Pure Zr-MOFs
Based on Meso-tetracarboxyphenylporphyrin. Inorg. Chem. 2019, 58,
5145−5153.
(36) Feng, D.; Gu, Z.-Y.; Li, J.-R.; Jiang, H.-L.; Wei, Z.; Zhou, H.-C.
Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal−Organic
Frameworks with Ultrahigh Stability as Biomimetic Catalysts. Angew.
Chem., Int. Ed. 2012, 51, 10307−10310.
(37) Xu, H.-Q.; Wang, K.; Ding, M.; Feng, D.; Jiang, H.-L.; Zhou,
H.-C. Seed-Mediated Synthesis of Metal−Organic Frameworks. J. Am.
Chem. Soc. 2016, 138, 5316−5320.
(38) Liu, Y.; Moon, S.-Y.; Hupp, J. T.; Farha, O. K. Dual-Function
Metal-Organic Framework as a Versatile Catalyst for Detoxifying
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DOI: 10.1021/acs.organomet.9b00273
Organometallics XXXX, XXX, XXX−XXX