Catalytically active metal organic framework based on a porphyrin modified by electron-withdrawing groups

Article abstract of DOI:10.1080/00958972.2016.1267728

One metal-free porphyrin, modified by electron-withdrawing groups, was synthesized by introduction of two peripheral pyridyl substituents and two metal coordination polymers, {[Zn(C₄₂H₁₆F₁₀N₆)]·2C₂H

Full text of DOI:10.1080/00958972.2016.1267728

Journal of Coordination Chemistry
ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: http://www.tandfonline.com/loi/gcoo20
Catalytically active metal organic framework
based on a porphyrin modified by electron-
withdrawing groups
Weixia Xu, Zengqi Zhang, Xin Zhao & Jun Li
To cite this article: Weixia Xu, Zengqi Zhang, Xin Zhao & Jun Li (2016): Catalytically active metal
organic framework based on a porphyrin modified by electron-withdrawing groups, Journal of
Coordination Chemistry, DOI: 10.1080/00958972.2016.1267728
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Date: 16 December 2016, At: 10:46

Publisher: Taylor & Francis
Journal: Journal of Coordination Chemistry
DOI: http://dx.doi.org/10.1080/00958972.2016.1267728
Catalytically active metal organic framework based on a porphyrin modified by
electron-withdrawing groups
#
#
WEIXIA XU †, ZENGQI ZHANG ‡§, XIN ZHAO‡ and JUN LI*‡
†
College of Chemistry and Chemical Engineering, Xianyang Nomal University, Xianyang, 712000,
People’s Republic of China
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education,
‡
College of Chemistry and Materials Science, Northwest University, Xi’an, Shaanxi 710069,
People’s Republic of China
§
Qingdao Institute of BioEnergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao,
Shandong 266101, People’s Republic of China
One metal free porphyrin, modified by electron-withdrawing groups, was synthesized by
introduction of two peripheral pyridyl substituents and two metal coordination polymers,
{
[Zn(C H F N )]·2C H N} (1) and {[Co(C H F N )]·C H N} (2), were synthesized
4
2
16 10
6
2
7
n
42 16 10
6
2
7
n
solvothermally. In 1, each porphyrin connected four other porphyrin complexes to construct a 2D
network through coordination bonds. Similarly, in 2 every Co(II) porphyrin coordinated with
four adjacent molecules to form a 2D framework. Thermogravimetric analyses indicate that both
1
and 2 show high thermal stabilities. The fluorescence data of 1 and 2 show that 1 may be a
candidate for potential inorganic-organic photoactive materials. Catalytic oxidation results show
that 2 displays high activity with the only product acetophenone quantitatively in 81.4%, and
after six cycles the catalytic activity slightly decreases. These features of 2, including the
*Corresponding author. Email: junli@nwu.edu.cn
#
These authors contributed equally to this work.
1

exceptional stability, and high catalytic activity, make it outstanding among MOFs reported in
the literature.
Keywords: Porphyrin; Crystal structure; Alkylbenzene oxidation; Catalytic activity
1
. Introduction
Metal-organic frameworks (MOFs), as a promising class of porous material, have attracted
attention for applications in various areas of catalysis, gas storage, luminescence, magnetism,
electrical conductivity, nonlinear optics and sensors [1-6]. One important application is catalysis;
the large internal surface and porosity make MOFs promising catalysts. Properties of MOFs can
be easily modified by tailoring the organic ligands and selecting the metal node [7-9], while that
of other porous materials are difficult to change. Using building blocks, such as porphyrin which
already have been proven effective as catalysts, is an attractive way to construct catalytic MOFs.
Porphyrin is a typical functional molecule and one of the most important molecules on
which life is based [10]. Its properties can be easily modified by changing peripheral substituents
and inserting metals into the center of the porphyrin ring [11]. Because of their functional
properties, porphyrins have been building blocks for construction of functional MOFs [12-21].
MOFs can enhance the efficiency of porphyrinic catalytic centers, as described in a previous
report [22]. Porphyrin with electron-withdrawing groups (such as fluorine) can greatly enhance
catalytic activity for oxidative reactions, so 5,15-(4-pyridyl)-10,20-(pentafluorophenyl)porphyrin
(H
2
Pp) was used to construct porphyrin-based MOFs. In 2009, Hupp et al. constructed
ZnPO-MOF by using 5,15-(4-pyridyl)-10,20-(pentafluorophenyl)porphyrin and
,2,4,5-tetrakis(4-carboxyphenyl)benzene as linker and Zn(II) as nodes, which could enhance
2400-fold rate of acyl-transfer reaction [23]. In spite of MOFs constructed from
,15-(4-pyridyl)-10,20-(pentafluorophenyl)porphyrin showing promising catalytic activities,
only three such MOFs have been reported [24, 25], and there is no paper that studies MOFs
1
~
5
2

constructed from H
Pp and exploit its catalytic activity, more H
In this contribution, two porphyrinic MOFs, ({[Zn(C H F N )]·2C H N} (1) and
2
Pp without ancillary ligands. To further discuss features of MOFs formed by
H
2
2
Pp based MOFs should be synthesized.
4
2
16 10
6
2
7
n
{
[Co(C H F N )]·C H N} (2), the C H N is dimethylamine molecule), are constructed based
4
2
16 10
6
2
7
n
2
7
upon H Pp. Single crystal XRD data indicate that 1 and 2 are isostructural; both crystallize in the
2
monoclinic system with C2/c space group and exhibit similar 2D layer structures. Their thermal
stability is explored by thermogravimetry (TG). Here we focus on their fluorescence properties
and catalytic activities to alkylbenzene oxidation. The results indicate that 2 exhibits high
catalytic activities to oxidation of ethylbenzene with 81.4% conversion, while activity of 1 to
ethylbenzene oxidation is only 20.1%.
2
2
. Experimental
.1. Synthesis of 5,15-(4-pyridyl)-10,20-(pentafluorophenyl)porphyrin (H Pp)
2
The method to generate H Pp was that reported [26, 27]; 0.80 g (7.37 mmol)
2
4
-pyridinecarboxaldehyde was mixed with 100 mL propionic acid. Then, 2.30 g (7.37 mmol)
meso-(pentafluorophenyl)dipyrrole dissolved in 15 mL propionic acid was added dropwise to the
mixture. The reaction mixture was heated at 145 °C for 50 min. After completing the reaction,
the solvent was removed under vacuum and 20 mL C H OH was added. Then the mixture was
2
5
cooled overnight and crude product precipitated. The crude product was purified by using silica
chromatography with dichloromethane and acetone (4:1) as eluent; the main purple band was
collected. After removing solvent, a purple-black solid of H
2
Pp was obtained. Yield: 5.8%.
m.p. >250 °C; Anal. Calcd. for C42 (Mol. wt: 796.14), %: C, 63.32; H, 2.28; N, 10.55.
18 10 6
H F N
+
1
Found: C, 63.25; H, 2.38; N, 10.62. MS, m/z: 797.2([M+1] ) amu. H NMR (400 MHz, CDCl ,
3
TMS), δ 9.01 (d, 4H, 2, 6-H on pyridine); 8.79-8.85 (dd, 8H, β-H on porphyrin), 8.10 (d, 4H, 3-H
on pyridine), -2.99 (s, 2H, NH). UV-vis (CHCl ) λmax/nm, 413 (Soret band), 509, 539, 584, 640
3
-1
(
Q bands). FT-IR ν, cm , 3437, 2923, 1650, 1596, 1521, 1499, 1403, 1348, 1149, 1072, 1046,
9
87, 922, 812, 778, 749, 730, 668.
3

At the next stage, 0.02 mmol (0.016 g) H Pp was dissolved in 8 mL mixture of
2
dichloromethane and 2 mL of ethanol, and then kept at room temperature; three days later, purple
prismatic crystals of H Pp were obtained.
2
2
.2. Synthesis of {[Zn(C H F N )] ·2 C H N} (1) and {[Co(C H F N )] ·C H N} (2)
4
2
16 10
6
2
7
n
42 16 10
6
2
7
n
A solution of H
2
Pp (0.015 mmol) and metal salts (Zn(NO
3
)
2
·4H
2
O or Co(NO
3
) ·6H
2
2
O)
(0.03 mmol) in 6 mL DMF (N,N-dimethylformamide) was transferred to a 25 mL
polytetrafluoroethylene lined stainless steel container. The vessel was then heated to 120 °C and
-1
kept for 96 h. After cooling to room temperature at 5 °C·h , purple prismatic crystals were
obtained. Crystals were very stable in air.
2
.2.1. {[Zn(C42
H
16
F
10
N
6
)]·2C
2
H
7
N} (1). Yield: 70.0%. Elemental analyses Calcd (%) for
n
C H F N Zn (905.06): C, 58.39; H, 2.56; N, 10.83. Found: C, 58.35; H, 2.62; N, 10.86.
44
23 10
7
-1
UV-Vis (CH Cl ) λ : 413 nm, 477 nm, 529 nm; IR(KBr) ν/ cm : 3431, 2932, 1600, 1474,
2
2
max
1
212, 975, 801, 564.
2
.2.2. {[Co(C42
H
16
F
10
N
6
)]·C
2
H
7
N} (2). Yield: 67.0% Elemental analyses Calcd (%) for
n
C H F N Co (898.62): C, 58.81; H, 2.58; N, 10.91. Found: C, 58.86; H, 2.62; N, 10.96.
44
23 10
7
-1
UV-Vis (CH Cl ) λ : 409 nm, 538 nm; IR(KBr) ν/ cm : 3435, 2925, 1600, 1485, 975, 797.
2
2
max
2
.3. Crystallographic data collection and refinement
Appropriate crystals were placed on a Bruker Smart Apex CCD crystal X-ray diffractometer with
graphite monochromated Mo K radiation (λ = 0.7107 Å) at 298 K. The structures were solved
α
2
by direct methods and refined by full-matrix least-squares on F using SHELXTL-97
crystallographic software package [28, 29]. All non-hydrogen atoms were refined with
anisotropic thermal parameters. The hydrogens were placed in calculated positions with fixed
C-H bond lengths. The crystal parameters of H
2
Pp, 1 and 2 are given in table 1.
4

2
.4. Typical procedure for catalytic oxidation
Alkylbenzene (0.1 mmol), tert-butylhydroperoxide (TBHP, 0.5 mmol), catalyst (0.005 mmol)
and H O (2.0 mL) were added into a flask and stirred at 80 °C for 20 h. When the reaction
2
finished, the identity of the product was determined by using gas chromatography (GC),
compared with authentic samples analyzed under the same conditions. The yield of product was
also obtained by GC analysis with a flame-ionization detector (FID) using a capillary SE-54
column.
3
3
. Results and discussion
.1. Crystal structure of H
2
Pp
The crystal structure of H
2
Pp is shown in figure 1a; crystal data and refinement parameters are
given in table 1. The single crystal X-ray diffraction analysis reveals that H Pp crystallizes in the
2
monoclinic space group C2/c. They have flexible central backbone and four peripherally
positioned binding sites oriented laterally in different directions. The porphyrin macrocycle in
H
2
Pp displays a planar configuration with four pyrrole rings almost coplanar. The dihedral
angles between the neighboring pyrrole rings in H Pp are 7.105°, 4.614°, 6.221° and 5.687°,
2
respectively. The distance between pyrrole nitrogen and porphyrin main plane (formed by 20 C
atoms) is within ±0.0143 Å, indicating that four nitrogens are almost coplanar.
Porphyrin molecules self-assemble through C-H···F interactions to form step-ladder
chains. The distance between two porphyrin macrocycle planes is 4.2777 Å. The chain further
connects to each other by π···π interactions between pyridine rings and C-H···F interactions to
construct a 3D supermolecular configuration.
In 1, the Zn(II) resides at the center of the porphyrin macrocycle by coordinating with
four pyrrole nitrogens and forms octahedral geometry through coordinating with two nitrogens of
two trans-pyridyl molecules in axial positions (figure 2a). The values of Zn-N bond lengths are
generally close. The displacement of each 20-membered ring atom is from -0.158(9) to
5

+
0.158(9) Å from the equatorial mean N4 plane, while that of four pyrrole nitrogens is 0 Å from
their mean N4 plane, indicating that atoms of the porphyrin macrocycle are almost coplanar.
Each porphyrin connects two adjacent units through coordination bonds formed by its
pyridyl substituents and Zn(II) of adjacent porphyrins, and it links another two porphyrins
through Zn(II) coordinating with pyridyl. Every porphyrin molecule connects four adjacent
molecules through coordination bonds to self-assemble into a two-dimensional (2D) layer
(figure 2b). The neighboring layers further packed into a 3D supermoleculer framework in a
parallel model with interlayer distance of adjacent layers about 12.2 Å (figure 2c). If porphyrin is
considered to be a four-connected node in the square geometry, the net of 1 can be simplified as a
4
2
{
4 6 } network (figure S1, Supporting Information). Because of the large size of the
square-planar molecules, the networks formed by porphyrin are porous. These voids account for
1.9% of the crystal volume and are accessible to guest solvent components (dimethylamine) as
1
estimated by PLATON analyses.
As shown in figure 3a, Co(II) coordinates with four nitrogens of the porphyrin
macrocycle and two pyridyl substituent groups to form an octahedral geometry. The atoms of the
porphyrin macrocycle are almost coplanar. The porphyrin connects two adjacent porphyrins
through coordination bonds between its pyridyl substituents and Co(II) of adjacent porphyrins,
and links another two porphyrins through Co(II) coordinating with pyridyl to form a 2D
metalloporphyrin framework (figure 3b). The 2D networks further arrange through π···π
interactions in ABAB stacking pattern (figure 3c), generating a microporous 3D supermolecular
structure with pore size of 7.9 × 7.9 Å. If one considers the porphyrin building block to be a
4
2
four-connected node, the net of 2 can then be rationalized as a {4 6 } network topology
(figure S2, Supporting Information). The potential solvent accessible void space accounts for
1
0.1% of the whole crystal volume as estimated by PLATON.
The frameworks of 1 and 2 are directly constructed through porphyrin units, which is
different from those observed in ZnPO-MOF [24], constructed from
,2,4,5-tetrakis(4-carboxyphenyl)benzene and 5,15-dipyridyl-10,20-bis(pentafluorophenyl)-
1
6

porphyrin. X-ray diffraction analysis shows that 1 and 2 are isostructural and have similar crystal
structures: first, both 1 and 2 crystallize in the monoclinic system with C2/c space group and
exhibit a 2D layer structure; second, the configuration of porphyrin units and the coordination
environment of metals in 1 and 2 are similar; third, there are the same solvent molecules
(
dimethylamine) in the pores of 1 and 2. The metal to metal distance between porphryin units in
different layers of 1 is 11.179 Å, while the distance for 2 is 11.979 Å, slightly shorter than that of
reported MOFs from H Pp [24]. Due to different metals in the macrocycle of porphyrin, the size
2
of pores in 1 and 2 are 9.9 × 9.9 Å and 7.9 × 7.9 Å, respectively, which lead to different potential
solvent accessible void space (11.9% for 1 and 10.1% for 2). Owing to different center metal of
porphyrin units in 1 and 2, which determine catalytic activity of MOFs, 1 and 2 show quite
different catalytic properties with conversion 20.1% for 1 and 81.4% for 2, respectively.
3
.2. Thermogravimetric analysis and powder XRD
Thermogravimetric analyses (TGA, figure S3) of 1 and 2 were performed by heating the samples
−
1
from 20 to 800 °C under N with a heating rate of 10 °C·min (figure S3a). There is 5% weight
2
loss from room temperature to 220 °C, corresponding to loss of dimethylamine and
decomposition of 1 framework occurred at 450 °C. For 2, 2.5% weight loss around 200 °C
corresponds to loss of two dimethylamine molecules, at 400 °C decomposition occurred. The
thermal behaviors characterized by TGA display that these two materials exhibit high thermal
stabilities. The phase purity for 1 and 2 is confirmed by powder X-ray diffraction (PXRD)
analysis in bulk (figure S4) with all of the measured peaks closely matching those in the
simulated pattern generated from the single-crystal XRD data, indicating that 1 and 2 retain the
crystalline nature and porous structure with the pores comparable to those revealed in the single
crystal.
7

3
.3. Fluorescence property
The fluorescence of 1 and 2 was examined in the solid state at room temperature as shown in
figure 4. Free H Pp displays two medium-intensity emission peaks at 665 and 708 nm upon
2
excitation at 424 nm. For 1, there is only one emission at 672 nm upon excitation at 368 nm,
which is ascribed to protonation of the ligand and the heavy-atom effect. After Zn ion inserts into
the porphyrin macrocycles, the N of pyrrole form coordination bonds with Zn(II) and Zn(II)
forms back donation π bond with nitrogens by donating electrons in d orbital. The formation of
back donation π bond between Zn(II) and porphyrin enhances the electrons density of porphyrin
macrocycle. Therefore, the symmetry and aromaticity of porphyrin macrocycle are decreased,
resulting in larger HOMO-LUMO energy gap, therefore blue-shifted peaks were observed
[30-32]. These results indicate that the emission behavior can be effectively modulated by
protonation and metal coordination, suggesting that 1 may be a candidate for potential hybrid
inorganic-organic photoactive materials.
3
.4. Catalytic activity
We examined 1 and 2 for their catalytic oxidation of ethylbenzene. The ethylbenzene oxidation
was performed using tert-butylhydroperoxide (TBHP) as the oxidant in H O at 80 °C, with GC
2
monitoring of reaction. The results (table 2) show that 2 efficiently catalyzes conversion of
ethylbenzene to acetophenone in 81.4% yield, while 1 shows negligible activity with conversion
of 20.1%. After reaction completion, solid 2 was easily recovered by centrifuging, and
subsequently used in successive runs with only slightly decreased product yields. The conversion
after three cycles is 74.5%. When the substrate was changed to 1-phenylpropane,
1
1
,2,3,4-tetrahydronaphthalene and diphenyl methane, the conversion decreased to 38.6, 43.7 and
5.6%, respectively. The catalytic activity of 2 is slightly lower than Mn(III)/Fe(III) porphyrin
MOFs in previous reports [15, 16, 33], with Mn(III)/Fe(III) exhibiting higher activity than that of
(Co(II)). However, the catalytic ability of 2 is superior to MOFs constructed by Co(II)
porphyrin [34].
2
8

4
. Conclusion
One metal free porphyrin, H
substituents and their two metal coordination polymers ({[Zn(C42
[Co(C H F N )]·C H N} (2)) were synthesized solvothermally. In both 1 and 2, each
2
Pp, was synthesized by the introduction of two peripheral pyridyl
)]·2C N} (1) and
H
16
F
10
N
6
2
H
7
n
{
4
2
16 10
6
2
7
n
porphyrin connected to four adjacent porphyrins to construct a 2D network through coordination
bonds. Thermogravimetric analyses indicated that 1 and 2 show high thermal stabilities.
1
exhibited strong luminescence, indicating it would be a good candidate for luminescent
materials. Catalytic oxidation results show that 2 displayed high catalytic activity with
acetophenone the only product in 81.4%; after six cycles the catalytic activity slightly decreases.
These features of 2 including the exceptional stability and catalytic activity make it outstanding
among the MOFs reported in the literature.
Acknowledgements
The authors acknowledge the research grant provided by the National Nature Science Foundation
of China (21271148, 21671158) that resulted in this article.
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11

Figure 1. (a) The molecular structure of H
c) supermolecular structure of H Pp.
2
Pp; (b) self-aggregated step-ladder;
(
2
12

Figure 2. (a) Zn(II) coordination environment of 1 (hydrogens are omitted for clarity). Symmetry
transformations used to generate equivalent atoms: a, -x+1/2,-y+3/2,-z; b, -x+1/2,y-1/2, -z+1/2; c,
x, -y+2, z-1/2). (b) 2D network in 1 (coordination environment around Zn ion is shown as
turquoise polyhedron). (c) Perspective views of the packing diagram of 1 along the a-axis. (All
hydrogens and solvent molecules are omitted for clarity.)
13

Figure 3. (a) Co(II) coordination environment of 2 (symmetry transformations used to generate
equivalent atoms: a, -x+1/2,-y+3/2,-z; b, -x+1/2,y-1/2,-z+1/2; c, x, -y+2, z-1/2). (b) 2D network
of 2 (coordination environment around Co is shown as violet polyhedron). (c) Packing
framework of 2 along the a-axis. (All hydrogens and solvent molecules are omitted for clarity.)
14

Figure 4. Photoluminescence spectra of H Pp, 1 and 2 in the solid state at room temperature.
2
15

Graphical abstract
1
6

Table 1. The crystal parameters of H Pp, 1 and 2.
2
H
2
Pp
1
2
Empirical formula
Formula weight
C H F N
C H F N Zn
C H F N Co
42
18 10
6
44 23 10
7
44 23 10
7
796.62
981137
Monoclinic
C2/c
20.598(6)
7.061(2)
23.997(7)
90
905.06
898.62
CCDC number
Crystal system
Space group
a (Å)
b (Å)
c (Å)
981135
Monoclinic
C2/c
23.107(5)
13.906(3)
14.106(3)
90
1448878
Monoclinic
C2/c
22.637(5)
14.201(3)
14.275(3)
90
α (°)
β (°)
91.832(7))
90
102.36(3)
90
102.71
90
γ (°)
3
V (Å )
3488.4(18)
4
4427.5(15)
4
4476.5(15)
2
Z
3
Dcalc (Mg/m )
10.538
10608
1.358
1.300
F(0 0 0)
1824
1760
-
1
μ (mm )
,wR [I >2σ(I)]
R , wR (all data)
1.599
0.635
0.461
R
1
2
0.0896, 0.2131
0.2024, 0.2877
1.147
0.1057, 0.3817
0.1094, 0.4028
1.065
0.1391, 0.3810
0.1910, 0.4443
1.049
1
2
2
GOOF (F )
17

a
Table 2. Selective oxidation of alkylbenzenes catalyzed by porphyrin complexes .
b
Entry
1
Substrate
Catalyst
Product
Conv. (%)
20.1
Select. (%)
99
1
2
2
3
4
5
6
7
8
2
81.4
74.5
38.6
15.6
43.7
2.7
99
99
99
99
82
75
71
-
c
2
2
2
2
ZnCl2
CoCl2
no
4.8
trace
a
Conditions: a mixture of catalyst (0.01 mmol), alkylbenzene (0.1 mmol), and TBHP
b
c
(0.5 mmol) in H O (2.0 mL) was stirred at 80 °C for 20 h. Based on GC analysis. The
2
sixth cycle.
18