A metal-metalloporphyrin framework based on an octatopic porphyrin ligand for chemical fixation of CO2 with aziridines

Article abstract of DOI:10.1039/c7cc08844b

A new porous metal-metalloporphyrin framework, MMPF-10, has been constructed from an octatopic porphyrin ligand, which links copper paddlewheel units to form a framework with fmj topology. In situ metallation of the porphyrin ligands provides MMPF-10 with two unique accessible Cu(ii) centers. This allows it to behave as an efficient Lewis acid catalyst in the first reported reaction of CO₂ with aziridines to synthesize oxazolidinones catalyzed by an MMPF.

Full text of DOI:10.1039/c7cc08844b

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A Metal-Metalloporphyrin Framework based on an Octatopic
Porphyrin Ligand for Chemical Fixation of CO with Aziridines
2
a,b,‡
b,‡
b
b
b
c
Xun Wang,
Wen-Yang Gao, Zheng Niu, Lukasz Wojtas, Jason A. Perman,* Yu-Sheng Chen,
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
b
Zhong Li,* Briana Aguila and Shengqian Ma*
DOI: 10.1039/x0xx00000x
www.rsc.org/
A new porous metal-metalloporphyrin framework, MMPF-10, has situ, or after the syntheses of these materials.14-15 Porphyrin
been constructed from an octatopic porphyrin ligand, which links ligands allow extra accessible metal sites (if not coordinated
copper paddlewheel units to form a framework with fmj topology. from other ligands) which will allow them to participate as
In-situ metallation of the porphyrin ligands renders MMPF-10 with catalytic sites similarly to naturally occurring systems.16,17 In
two unique accessible Cu(II) centers. This allows it to behave as an addition, porphyrin molecules are chemically modifiable and
efficient Lewis acid catalyst in the first reported reaction of CO
2
their dimensions or chemical functionality can be altered at the
with aziridines to synthesize oxazolidinones catalyzed by a MMPF. meso-positions. The resulting MMPF synthesized from larger
porphyrin molecules could possess bigger pores that would help
facilitate both faster diffusion of substrates and larger substrates
to reach the many reactive centers within a porous framework to
enhance its catalytic activity.17,18
Given the competitive nature to outperform traditional porous
materials, such as zeolites and carbonaceous materials for their
porous properties, a rise in the use of metal-organic frameworks
1
(
MOFs) are prevalent in the scientific literature. These materials
Many MOFs, particularly MMPFs, have been used as
are designed and synthesized from metal ions/clusters and
organic molecules (participating as nodes and spacers),1-2 that
have shown higher tunability than their strictly inorganic or
carbonaceous counterparts  in part due to the large assortment
of reagents. Desired structures are obtainable by the judicious
selection of reagents, followed by appropriate reaction
heterogeneous Lewis-acid catalysts for CO
2
chemical
transformation reactions with epoxides to form cyclic
carbonates.16, 19-20 A class of heterocyclic chemicals, similar to
epoxides, aziridines,21 allows the cycloaddition reactions with
to form oxazolidinones.22-24 This class of compound is
CO
2
particularly important for use in antimicrobial agents such as
tedizolid,25-26 linezolid,27-28 and radezolid.29-30 Previously,
3
conditions. Once synthesized, the organic ligands or metal ions
can be modified by post-synthetic procedures to impart new
physical or chemical properties in the materials.4
homogenous catalysts have shown good abilities to convert CO
2
and aziridines into oxazolidinones.31-33 However, these catalysts
As an important subclass of MOFs, metal-metalloporphyrin
frameworks (MMPFs) have attracted an increasing amount of
can’t be easily recycled, thus bringing about a need for new
5
attention because they have shown to perform well in
applications of gas storage/separation,6-7 catalysis,8-9
photochemistry,10-11 and additional areas of research.12-13
MMPFs can possess mono-, bi- or multi-metallic systems
because the porphyrin molecule can be metallated before, or in-
a.School of Chemistry and Chemical Engineering, South China University of
Technology, Guangzhou 510640, P.R. China. E-mail address: cezhli@scut.edu.cn
b.
Department of Chemistry, University of South Florida, 4202 East Flower Avenue,
Tampa, Florida 33620, USA. E-mail: sqma@usf.edu ; Fax: +1-813-974 3203;
Tel: +1-813-974 5217
ChemMatCARS, Center for Advanced Radiation Sources, The University of
c.
Fig. 1 (a) tetrakis-3,5-bis[(4-carboxy)phenyl]phenyl porphine
Chicago, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
Electronic supplementary information (ESI) available: Experimental details,
(
H
10TBCPPP); (b) copper paddlewheel SBU (turquoise, copper;
†
torsion angles figures, XRD patterns and single-crystal data. CCDC 1580770. For
ESI and crystallographic data in CIF or other electronic format see DOI:
XXXX/XXXXXX
red, oxygen; grey, carbon)
‡
These authors contributed equally to this work
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DOI: 10.1039/C7CC08844B
Fig. 3 (a) (3, 4, 4)-connected network of MMPF-10 (blue points,
porphyrins; yellow points, paddlewheels; pink points, terphenyl
arms). (b) N adsorption isotherm of MMPF-10 at 77 K.
2
This difference in torsion angle results in a different pore
structure of MMPF-10 (Fig. 2). The primary elongated
hexagonal channels are observed along the c-axis and shown
from the side view (Fig. 2a and 2c). This channel is generated
from a ring of four metellated porphyrin ligands and four copper
paddlewheels, which form a channel with cross-sectional
dimensions of 25.6×15.6 Å, measured between pyrrole carbon
atoms and two meso-substituent phenyl rings. The secondary
cavity is enclosed by a porphryin’s meso side arm coordinating
with four copper paddlewheels and a porphyrin base, exhibiting
a pentagonal-like windows and a cavity suitable to fit a sphere
with a diameter of 11 Å. (Fig. 2b). The free space in the fully
desolvated MMPF-10 calculated by PLATON is 79.6% of the
total crystal volume, which is comparable with 79.4% of PCN-
Fig. 2 (a) Hexagonal channel of MMPF-10 viewed along c-axis;
(b) pentagonal cavity of MMPF-10; (c) side view of the
hexagonal channel (turquoise, copper; red, oxygen; grey, carbon;
blue, nitrogen)
heterogeneous catalysts to perform as well or better than
homogeneous catalysts. Comparably, only a few heterogeneous
catalysts have been reported for this reaction.34-36 To the best of
our knowledge, MMPFs have not been used as a catalyst for CO
cycloaddition reactions with aziridines.
In this work, we report a porous metal-metalloporphyrin
framework, MMPF-10, which is constructed from an octatopic
ligand, tetrakis-3,5-bis[(4-carboxy)phenyl]phenyl porphine
2
22, a typical porphyrin-based MOFs, and is slightly higher than
2
the 78.0% free space of UNLFPF-1.6
Phase purity of MMPF-10 was confirmed by powder X-ray
diffraction (PXRD) studies, which show good agreement with
the calculated diffraction pattern (Fig. S6). Its permanent
porosity was evaluated through N
K after samples were activated using supercritical CO
2
isotherm measurement at 77
(ESI ).
(H10TBCPPP, Fig. 1a) and the copper paddlewheel building
block (Fig. 1b). With the inclusion of Cu(II) as a Lewis Acid
catalytic site, we explored this material’s performance in the
2
†
A type I adsorption isotherm was observed for MMPF-10 that
3
-
confirmed its microporous nature, with an uptake of ~120 cm g
cycloaddition reactions between aziridine and CO
Dark red block-shaped crystals of MMPF-10 were obtained by
solvothermal reaction of H10TBCPPP and Cu(NO ·2.5H O in
N,N-Dimethylacetamide (DMA) at 65 C (ESI ). Single crystal
X-ray diffraction analysis revealed that MMPF-10
Cu (CuTBCPPP)(H O) ] crystallized in the orthorhombic
2
.
1
at the saturated pressure (Fig. 3b). Derived from the N
2
adsorption isotherm, MMPF-10 possesses a Brunauer-Emmett-
3
)
2
2
2
-1
Teller (BET) surface area of ~419 m g (corresponding to a
†
2
-1
Langmuir surface area of ~478 m g ).
Albeit MMPFs have shown high catalytic activity in
[
4
2
4
cycloaddition reactions between CO
not been explored to catalyze the reaction between aziridines and
CO . Table 1 (entries 1 ~ 3) shows the catalytic results from the
aziridines cycloaddition under 1 bar of CO at room temperature.
MMPF-10 displayed moderate catalytic activity for
cycloaddition of 1-methyl-2-phenylaziridine to form 3-methyl-
-phenyl-2-oxazolidinone with a yield of 63% (Table 1, entry 1),
2
and epoxides, they have
Immm space group with a = 26.294(4) Å and c = 34.046(6) Å.
Each copper paddlewheel is connected with four porphyrin
ligands, which in turn connect to eight copper paddlewheels
producing a 3D non-interpenetrated structure. When assuming
the copper paddlewheel to be a 4-connected node and the
porphyrin ligand to be one 4-connected node (porphyrin ring)
and four 3-connected nodes (terphenyl arm), MMPF-10 displays
a (3,4,4)-connected network with topology of fmj (Fig. 3a),
2
2
a
5
which was higher than 47% for HKUST-1 under similar reaction
conditions. (Table 1, entry 2). The higher catalytic activity for
MMPF-10 compared with HKUST-1 could be presumably
ascribed to the higher propensity for aziridines situated near the
easier accessible Lewis-acid Cu(II) sites in the metallated
6
which differs from the fjh topology of UNLFPF-1 constructed
from the same porphyrin ligand joined with the zinc
paddlewheel. The differences between these two materials can
be attributed to the torsion angle between the porphyrin ring and
its meso-substituent phenyl rings. The torsion angles are 92.92
porphyrin ring, which are activated then followed by attack of
-
molecules.18, 36, 37
Br from nBu
4
NBr and reaction with CO
2
for MMPF-10 and 117.06 for UNLFPF-1 (Fig. S4~S5, ESI†).
2
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paddlewheel building blocks. MMPF-10 showVeiedw ArdtiicflefeOrnelinnet
DOI: 10.1039/C7CC08844B
topology from UNLFPF-1 because of the differences in the
Table 1. Cycloaddition Reactions of different substituted
torsion angle of the porphyrin’s meso-substituents, resulting in a
network of fmj topology. Both the copper paddlewheel building
blocks and the copper metallated porphyrin ligand, played
important roles for showing catalytic activity on the chemical
2
aziridines with CO catalyzed by MOFs
fixation of CO
2
with aziridines to form oxazolidinones.
Additional research is being explored in our group to find
methods to maintain the high yields while working at 1 bar of
CO
2
2
CO pressure.
Entry
Substrate
Yield(%)
Pressure(MPa)
The authors acknowledge the China Scholarship Council
CSC), Key Program of National Natural Science Foundation of
(
1a
0.1
63
China (No. 21436005), National Natural Science Foundation of
China (No. U1662136) and the United States National Science
Foundation (DMR-1352065) and the University of South Florida
2b
3c
4c
5c
0.1
2
47
>99
99
(
USF) for financial support of this work.
Notes and references
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Reaction conditions: aziridine (1mmol), MMPF-10 (0.625 mol% based on
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A new porous metal-metalloporphyrin framework,
MMPF-10, was synthesized for CO2 cycloaddition with
aziridines.
4
| J. Name., 2012, 00, 1-3
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