Permanently porous Co(II) porphyrin-based hydrogen bonded framework for gas adsorption and catalysis

Article abstract of DOI:10.1021/acs.cgd.5b00987

A new microporous hydrogen-bonded organic framework (HOF) based on a cobalt(II) porphyrin, namely, Co(II) 5,10,15,20-tetra(4-(4-acetateethyl)phenoxy)phenylporphyrin (1), has been synthesized and structurally characterized. Single crystal X-ray diffraction

Full text of DOI:10.1021/acs.cgd.5b00987

Article
pubs.acs.org/crystal
Permanently Porous Co(II) Porphyrin-Based Hydrogen Bonded
Framework for Gas Adsorption and Catalysis
Zengqi Zhang, Jun Li,* Yahong Yao, and Shu Sun
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
S
* Supporting Information
ABSTRACT: A new microporous hydrogen-bonded organic framework
(HOF) based on a cobalt(II) porphyrin, namely, Co(II) 5,10,15,20-tetra(4-
(4-acetateethyl)phenoxy)phenylporphyrin (1), has been synthesized and
structurally characterized. Single crystal X-ray diffraction analysis reveals that
porphyrin molecules connect each other by intermolecular hydrogen bonds to
form 2D layer, and the 2D layer further links though π···π interactions to form
3D supramolecular structure, exhibiting one kind of micropore with 3.98 ×
6.47 Å2. The HOF of 1 exhibits not only a permanent porosity with the
Langmuir surface areas of 158.79 m2·g−1, and the Brunauer−Emmett−Teller
surface areas of 97.70 m2·g−1, but also, more importantly, high catalytic
efficiency and selectivity for oxidation of ethylbenzene to acetophenone in
quantitative 83.1% yield.
property, and strong optical absorption and emission.26−33
1. INTRODUCTION
Because of their desirable functional properties, porphyrins
Because porous materials have very important and useful
have been ideal building blocks for construction of functional
application in gas storage, separation, catalysis, and electro-
MOFs, and hundreds of porphyrin based MOFs have been
des,1−5 they have attracted extensive research attention to
reported from the 1990s.34−44 Although porphyrin super-
target such materials for highly efficient gas storage and
molecular structure connected by hydrogen-bonding inter-
catalysis. Such efforts eventually lead to the emergence of
actions have been widely studied,45−48 porphyrin based HOF
porous metal organic frameworks (MOFs). During the past two
exhibiting permanent porosity had not been studied until 2015
decades, a lot of porous MOFs have been prepared by self-
when Banglin Chen reported a HOF constructed by 2,4-
assembly of metal and organic ligand, such as excellent work by
diaminotriazinyl functionalized porphyrin compound; to the
the Xiaoming Chen group and the Jing Li group in such areas
best of our knowledge, this is the only reported porphyrin
in the past years.6−15 Compared with MOFs, porous hydrogen-
based HOF.49 Herein, we report a new porphyrin-based HOF 1
bonded organic frameworks (HOFs) have lagged significantly
constructed from Co(II) 5,10,15,20-tetra(4-(4-acetateethyl)-
behind. HOFs, which are quite different from MOFs, are
phenoxy)phenylporphyrin (CoTCPp) and permanent porosity
directly self-assembled from organic building blocks via weak
of 1 was confirmed by gas sorption isotherms. In addition,
hydrogen-bonding interactions. Although HOFs have been
catalytic activity to ethylbenzene oxidation of HOF 1 was first
proposed as potential porous materials for about the past two
evaluated.
decades as well,16,17 only very few HOFs exhibiting permanent
porosity have been reported in recent years.18−23 Such a
situation is mainly due to hydrogen-bonding interactions which
are typically too weak to stabilize the frameworks and establish
permanent porosities. In other words, the supermolecular
2. EXPERIMENTAL SECTION
2.1. Materials and Instruments. 4-Fluorobenzaldehyde and
ethyl-p-hydroxybenzoate were purchased from Sigma-Aldrich Japan
(Chiba, Japan); other reagents were purchased from Beijing Chemical
structure is usually broken and HOFs collapse when solvent
Reagents Company; all solvents and reagents were used without
guests are removed. Unlike MOFs, HOFs have advantages of
solution processability and easy purification and can be easily
recovered by recrystallization, making them promising func-
tional materials.
further purification, except pyrrole, which was distilled before use.
IR spectra were obtained with samples in KBr for the title
complexes on A BEQUZNDX-550 series FT-IR spectrophotometer in
the range 4000−400 cm−1. UV−vis spectra were performed by a
Shimadzu UV1800 UV−vis spectrophotometer. 1H NMR spectra were
collected in deuterated chloroform (CDCl3) using a Bruker AC-400 at
Porphyrin is a typical functional discotic molecule and its
properities can be easily modified by introduction of peripheral
substituent in porphyrin and insertion of metal atoms into the
center of the porphyrin ring.24,25 In the past decade, porphyrin
has attracted great research attention as a versatile synthetic
base for various materials due to their rich electronic, catalytic
Received: July 14, 2015
Revised: September 2, 2015
© XXXX American Chemical Society
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Scheme 1. (a) Syntheses of the 4-(4-Formylphenoxy)ethylbenzoate. (b) Syntheses of 5,10,15,20-Tetra(4-(4-
acetateethyl)phenoxy)phenyl porphyrin (H2TAPp) and 5,10,15,20-Tetra(4-(4-carboxyl)phenoxy)phenyl porphyrin (H2TCPp)
room temperature and chemical shifts were reported in ppm units with
respect to the reference frequency of TMS. Mass spectrometry (MS)
analysis was carried out on a matrix assisted laser desorption/
ionization time-of-flight mass spectrometer (MALDI-TOF MS, Krato
Analytical Company of Shimadzu Biotech, Manchester, Britain) using
a standard procedure involving 1 mL of the sample solution.
2.2. Synthesis. The synthetic routes to the porphyrin and
metalloporphyrins are shown in Scheme 1.
2.2.1. Synthesis of 4-(4-Formylphenoxy)ethylbenzoate. The
synthetic method used in our study was presented in the previous
report.50 In a 100 mL three-necked flask, ethyl-p-hydroxybenzoate (17
mmol), 4-fluorobenzaldehyde (17 mmol), and K2CO3 reacted in
refluxing 30 mL N,N-dimethylformamide (DMF) for 3 h. After being
cooled to room temperature, the reaction mixture was quenched with
water and extracted with CH2Cl2. The organic layer was washed with
water, dried over Na2SO4, and evaporated. The desired solid was
obtained. Yield: 52%. MS: m/z 271.10 ([M + H]+) amu. Mp: 55 °C.
FT-IR: υ, cm−1, 3420, 2848, 2753, 1721, 1396, 1367, 1236, 1167, 1097,
836, 698.
and then the solution was added in a polytetrafluoroethylene lined
stainless steel container. The container was gradually heated to 150 °C
in 4 h and kept for 3 days, then the crude products gradually cooled to
room temperature. The desired purple crystal [Co(C72H44N4O12)]·
2DMF (1) was obtained in 67% yield. Calcd for C78H44CoN6O14: C,
69.49; H, 3.29; N, 6.23%. Found: C, 69.57; H, 3.34; N, 6.27%. UV−
vis-DRS: λmax/nm, 423 (Soret band), 535 (Q-band). IR spectrum
(KBr, v/cm−1): 1643, 1400, 1236, 1164, 998, 803, 768.
2.2.5. Crystallographic Data Collection and Refinement. The
crystallographic data of 1 were obtained at 173 K with a Bruker
SMART CCD diffractometer with graphite monochromated Mo Kα
radiation (λ = 0.71073 Å). Absorption corrections were applied using
SADABS program.52 The structure was solved by direct method and
refined by full-matrix least-squares techniques using the SHELXL-97
program.53 Anisotropic thermal parameters were assigned to all non-
hydrogen atoms. Hydrogen atoms were placed in geometrically
calculated positions.
2.2.6. Typical Procedure Catalytic Oxidation. A mixture of
alkylbenzene (0.1 mmol), tert-butylhydroperoxide (TBHP, 0.5
mmol), catalyst (0.005 mmol), and acetonitrile (2.0 mL) was stirred
at 80 °C for 20 h. After the reaction, the identity of the product was
determined by using gas chromatography (GC), compared with the
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.
2.2.2. Synthesis of 5,10,15,20-Tetra(4-(4-acetateethyl)phenoxy)-
phenyl porphyrin (H2TAPp). The synthetic method used in our study
was the well-known Adler-Longo method.51 4-(4-Formylphenoxy)-
ethylbenzoate (12 mmol) and pyrrole (12 mmol) were reacted in
refluxing propionic acid for 50 min. The crude product was purified on
a silica-gel column with dichloromethane as eluent, and a desired
purple solid of compound H2TAPp was obtained. Yield: 6.2%. Mp:
>250 °C, UV−vis (CH2Cl2): λmax/nm, 418 (Soret band), 515, 551,
585, 650 (Q bands). FT-IR: υ, cm−1, 1711, 1587, 1500, 1231, 1160,
1098, 967, 874, 797. Anal. Calcd (found) for C80H62N4O12 (mol wt
1270.44) %: C, 75.58 (75.54); H, 4.92 (4.93); N, 4.41 (4.45). MS: m/
3. RESULTS AND DISCUSSION
3.1. Crystal Structure. Single-crystal X-ray diffraction
analysis reveals that 1 belongs to the triclinic system with
1
z 1271.40 ([M + H]+) amu. H NMR (CDCl3, 400 MHz): δ, ppm
space group P1. As shown in Figure 1, Co(II) coordinates with
̅
8.95 (s, 8H, β position of the pyrrole moiety), 8.22 (dd, J = 14.6, 8.3
Hz, 14H, Ar), 7.41 (dd, J = 48.4, 8.2 Hz, 18H, Ar), 4.43 (dd, J = 14.0,
6.9 Hz, 8H, −CH2), 1.45 (t, J = 7.0 Hz, 12H,-CH3), −2.75 (s, 2H,
NH).
four N atoms of porphyrin to form a square geometry. The
distance of Co−N [1.96(7)−1.97(7) Å] are in the normal
range for the similar porphyrin based Co(II) compounds,54,55
and slight longer than Co−N length in Co(III) porphyrin
crystal.56 The displacement of each 20-membered ring atom is
in the range of −0.057(3) to +0.057(3) Å from the equatorial
mean N4 plane, while that of four pyrrole N atoms is 0 Å from
their mean N4 plane, indicating that atoms of porphyrin
macrocycle are perfectly coplanar.
2.2.3. Synthesis of 5,10,15,20-Tetra(4-(4-carboxyl)phenoxy)-
phenyl porphyrin (H2TCPp). H2TAPp (0.1 g) was dissolved in 15
mL tetrahydrofuran, and 20 mL alkaline aqueous solution (KOH, 1
mol/L) was added. Then the mixture was stirring under reflux for 30h.
After being cooled to room temperature, HCl was added and the
desired solid powder precipitated. Yield: 6.2%. Mp: > 250 °C, UV−vis
(CH2Cl2): λmax/nm, 419 (Soret band), 516, 550, 592, 648 (Q bands).
FT-IR: υ, cm−1, 3029, 1708, 1597, 1498, 1236, 1164, 1093, 967, 874,
797. Anal. Calcd (found) for C72H46N4O12 (mol. wt: 1158.31), %: C,
74.60 (74.57); H, 4.00 (4.02); N, 4.41 (4.47). MS: m/z 1157.30 ([M-
H]−) amu.
In structure 1, each Co(II) porphyrin molecule connects
with four other porphyrin molecules through hydrogen bond
interactions formed by carboxy groups of two porphyirns, and
Co(II) porphyrin molecules are further self-assembled into a
two-dimensional (2D) supramolecular layer (Figure 2a). The
neighboring layers are packed into a 3D framework via the
2.2.4. Synthesis of [Co(C72H44N4O12)]·2DMF (1). 7 mg H2TCPP
and 10 mg CoCl2 was dissolved in 2 mL DMF and 1 mL HCOOH,
B
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3.2. Powder XRD and Thermogravimetric Analysis.
The phase purity for 1 is confirmed by powder X-ray diffraction
(PXRD) analysis in bulk (Figure 3). The evacuated samples are
Figure 1. Molecular structure of the organic building block for
construction of 1.
Figure 3. Powder X-ray diffraction patterns of 1, 1a, and recovered 1.
intermolecular C−H···π interactions between phenyl and
porphyrin macrocycle (shown in Figure 2b), generating a
microporous structure with the pore size of 3.98 × 6.47 Å
(Figure 2c,d). If one considers the porphyrin building block to
be a four-connected node in the square geometry, the net of 1
can then be rationalized as a sql {4462} network topology
(Figure S1, Supporting Information). The potential solvent
accessible void space accounts for approximately 18.90% of the
whole crystal volume as estimated by PLATONN.
obtained through heating under vacuum at 80 °C for 8 h.
PXRD results show that all of the measured peaks closely
matched those in the simulated pattern generated from the
single-crystal XRD data, indicating that after being heated for 8
h, 1 retains the crystalline nature and porous structure with the
pores comparable to those revealed in the single crystal. To
study the thermal stability of 1, thermogravimetric analysis
Figure 2. (a) Hydrogen bond interaction in structure of 1 (hydrogen atoms were omitted for clearity; the hydrogen bonds were shown as dotted
line). (b) Intermolecular π···π interaction between two porphyrin molecules (peripheral substituents were omitted for clearity; the C−H···π
interactions were shown as dotted line). (c) 3D packing framework. (d) Rhombic channels in 1 view along the a axis with an approximate dimension
of 3.98 × 6.47 Å2.
C
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Figure 4. (a) CO2 sorption isotherms of 1a at 273 and 298 K (solid symbols: adsorption; open symbols: desorption). (b) Isosteric heat of CO2
adsorption for 1a estimated by the virial equation.
Table 1. Selective Oxidation of Alkylbenzenes Catalyzed by Porphyrins
a
Conditions: a mixture of catalyst (0.005 mmol), alkylbenzene (0.1 mmol), and TBHP (0.5 mmol) in acetonitriler (2.0 mL) was stirred at 80 °C for
b
c
d
20 h. Based on GC analysis. Third cycle. Sixth cycle.
(TGA, Figure S2 in Supporting Information) is carried out in
the temperature range from 25 to 800 °C under a flow of N2
with a heating rate of 10 °C·min−1. Thermogravimetric analysis
of 1 reveals that there is a weight loss of 10.05% from room
temperature to 220 °C, corresponding to two guest N,N-
dimethylformamide (DMF) molecules in the pore of 1. Then,
the curve is followed by a relatively steady platform up to 400
°C; after this, the framework starts to decompose.
Before performing the adsorption property test, the guest
DMF molecules in 1 are removed by solvent exchange with
acetone; and the resulting samples are further activated at 80
°C to generate the activated HOF material (1a). The TGA
curve of 1a, shown in Figure S2 of the Supporting Information,
shows that there is a platform without weight loss in the
temperature range from room temperature to 400 °C,
indicating all solvent molecules have been removed. The
PXRD pattern of 1a (Figure 3) is only slightly shifted from that
of the as-synthesized 1 crystal, which is the result of the
flexibility and shrinkage of the framework. The PXRD data
indicate that the desolvated framework is obtained.
3.3. Gas Adsorption. To confirm the permanent micro-
porosity of the HOF 1a, gas-adsorption measurements (N2 and
CO2) of 1a was performed. The N2 sorption experiment of 1a
at 77 K shows type I adsorption isotherm behavior (Figure S3)
with apparent Langmuir surface areas of 158.79 m2·g−1 and
Brunauer−Emmett−Teller (BET) surface areas of 97.70 m2·
D
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g−1, respectively. The BET surface area of 1a is slightly smaller
than those microporpous porphyrin-based MOFs with the 2D
layered configurations.57,58 There is adsorption−desorption
hysteresis on the N2 sorption curve, indicating the existence of
micropores in 1a. The experimental pore size distribution
(PSD) is shown in Figure S4 of Supporting Information. The
median pore width is 0.99 nm and maximum pore volume is
0.052 cm3·g−1.
ASSOCIATED CONTENT
* Supporting Information
Refer to CCDC 1411460 for crystallographic data in CIF
format. The Supporting Information is available free of charge
on the ACS Publications website at DOI: 10.1021/
acs.cgd.5b00987.
■
S
TGA, N2 sorption isotherms, crystallographic data
(PDF)
The CO2 sorption properties on desolvated 1a at two
different temperatures (273 and 298 K) were also evaluated. As
shown in Figure 4a, the CO2 adsorption isotherms of 1a at both
273 and 298 K are nonclassical type I adsorption isotherms and
the CO2 uptakes are 42.18 cm3·g−1 (8.28 wt %) and 30.19 cm3·
g−1 (5.93 wt %) at 273 and 298 K, respectively. It is obvious
that the final CO2 uptake values of 1a at both 273 and 298 K
are higher than reported porphyrin based HOF,49 which is
comparable to some previously reported MOFs.59 All sorption
isotherms of 1a at 273 and 298 K show hysteresis. In order to
further study gas sorption behaviors of 1a, the adsorption
enthalpy of the HOF 1a to CO2 molecules (Figure 4b) was
calculated according to the CO2 gas adsorption isotherms at
273 and 298 K, utilizing a built-in function in Micromeritics
ASAP 2020 analyzer based on the Virial equation (shown in the
Figure S5, Supporting Information). The fitted enthalpy of CO2
adsorption for 1a at zero coverage is 23.20 KJ·mol−1, which is
comparable to those found in MOFs with small pores.60
3.4. Catalytic Activity of 1. We examined 1 for its catalytic
oxidation to ethylbenzene. The ethylbenzene oxidation was
performed in solvent of acetonitriler at 80 °C using tert-
butylhydroperoxide (TBHP) as the oxidant, with GC
monitored throughout the reaction. The results (Table 1)
show that 1 efficiently catalyzes the conversion of ethylbenzene
to the only product acetophenone quantitatively in 83.1% yield.
After reaction finished, solid 1 was easily recovered by
centrifuging and filtration (Figure S6 of Supporting Informa-
tion) and subsequently used in successive runs with only
slightly decreased product yields. The conversion after six
cycles is 72.7%. When the substrate was changed to 1-
phenylpropane, 1,2,3,4-tetrahydronaphthalene, and diphenyl-
methane, the conversion was decreased to 35.8%, 75.1%, and
24.8%, respectively. There is no obvious change in the P-XRD
pattern (Figure 3) except that peaks at 2θ = 19° and 2θ = 21°
disappeared in the curve of recovered 1, indicating that the
framework and pore are kept after the reaction.
AUTHOR INFORMATION
Corresponding Author
*E-mail: junli@nwu.edu.cn.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work has been supported by the NNSF (No. 21271148).
We are very grateful to Shaanxi Normal University for their
kind assistance.
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DOI: 10.1021/acs.cgd.5b00987
Cryst. Growth Des. XXXX, XXX, XXX−XXX