Metalation of a Mesoporous Three-Dimensional Covalent Organic Framework

Article abstract of DOI:10.1021/jacs.6b10316

Constructing metalated three-dimensional (3D) covalent organic frameworks is a challenging synthetic task. Herein, we report the synthesis and characterization of a highly porous (SA_BET = 5083 m² g^-1) 3D COF with a record low density (0.13 g cm^-3) containing π-electron conjugated dehydrobenzoannulene (DBA) units. Metalation of DBA-3D-COF 1 with Ni to produce Ni-DBA-3D-COF results in a minimal reduction in the surface area (SA_BET = 4763 m² g^-1) of the material due to the incorporation of the metal within the cavity of the DBA units, and retention of crystallinity. Both 3D DBA-COFs also display great uptake capacities for ethane and ethylene gas.

Full text of DOI:10.1021/jacs.6b10316

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Communication
Metalation of a Mesoporous Three-Dimensional Covalent Organic Framework
Luke A. Baldwin, Jonathan W. Crowe, David A. Pyles, and Psaras L. McGrier
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b10316 • Publication Date (Web): 04 Nov 2016
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Metalation of a Mesoporous Three-Dimensional Covalent Organic
Framework
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Luke A. Baldwin, Jonathan W. Crowe, David A. Pyles, Psaras L. McGrier*
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio, 43210, United States
Supporting Information Placeholder
Scheme 1. Synthesis of DBA-3D-COF 1 Using TBPM
and DBA[12] Units Followed by Metalation with
Ni(COD)2 to Produce Ni-DBA-3D-COF.
ABSTRACT Constructing metalated three-dimensional (3D)
covalent organic frameworks is a challenging synthetic task.
Herein, we report the synthesis and characterization of a high-
2
-1
ly porous (SABET = 5083 m g ) 3D COF with a record low
-3
HO
HO
OH
OH
density (0.13 g cm ) containing π-electron conjugated dehy-
O
O
O
O
B
B
drobenzoannulene (DBA) units. Metalation of DBA-3D-COF
1 with Ni to produce Ni-DBA-3D-COF results in a minimal
O
O
DBA[12]
B
B
O
O
2
-1
HO
OH
O
O
reduction in the surface area (SABET = 4763 m g ) of the ma-
terial due to the incorporation of the metal within the cavity of
the DBA units, and retention of crystallinity. Both 3D DBA-
COFs also display great uptake capacities for ethane and eth-
ylene gas.
B
O
B
O
B
O
B
O
O
O
+
10:1 Dioxane / Mesitylene
95 °C / 3 days
HO OH
B
HO
B
OH
B
OH
O
O
HO
B
O
B
TBPM
O
HO
B
OH
O
B
O
B
O
O
O
O
O
O
B
B
= Ni(0)
O
O
1-4
Covalent organic frameworks (COFs) are an exceptional
B
B
O
O
O
O
class of porous crystalline materials that possess low densities,
great thermal stabilities, and high internal surface areas. Over
the past decade, these characteristics have made COFs attrac-
B
O
B
O
B
O
B
O
O
O
Ni(COD)2
Toluene
5,6
O
O
tive candidates for applications related to gas storage, sepa-
B
7,8
9-13
14,15
O
B
rations, optoelectronics,
age.
catalysis,
and energy stor-
O
16,17
The modular nature of COFs provides a unique plat-
O
B
O
B
O
O
form to incorporate various rigid molecular building blocks
18
that can be metalated to enhance their catalytic and gas ad-
19,20,21
sorption properties.
While the construction of two-
22
dimensional (2D) COFs containing metalated porphyrin,
phthalocyanine, and bipyridine units have become fairly
34,
state transition metals. The planarity and metal binding
properties of DBAs are comparable to porphyrin and
phthalocyanine ligands, which typically use hard nitrogen
atoms to bind metals. In contrast, DBAs are neutral com-
pounds that contain soft ligands capable of donating 2-4 elec-
trons per alkyne depending on the electronic demands of the
23
24
prevalent, finding efficient ways to synthesize novel three-
25-28
dimensional (3D)
COFs that can be metalated without
compromising the surface area or pore volume of the material
is still a challenge. As a consequence, only one metalated 3D
29
COF has been reported. The limited number of metalated
35
metals. We demonstrate that DBA[12] and TBPM mono-
mers can be utilized to form a crystalline 3D polymer network
with the lowest density (0.13 g cm ) and highest BET surface
area (5083 m g ) reported to date for a COF. We also show
that the metalation of DBA-3D-COF 1 with Ni(COD)2 to ob-
tain Ni-DBA-3D-COF results in a minimal reduction in the
pore volume and surface area of the material. Interestingly,
both materials display great uptake capacities for ethane and
ethylene gas.
3D COFs is likely attributed to the synthetic challenge of uti-
lizing the right geometrically shaped monomers that can not
only produce crystalline polymeric networks but also form
strong complexes with metal ions. Finding monomers that can
accomplish this task would be essential for constructing light-
weight crystalline materials that could potentially rival their
-3
2
-1
30
metal-organic framework (MOF) counterparts.
Herein, we present the synthesis and metalation of a meso-
porous 3D COF containing C3-symmetric π-electron conju-
gated dehydrobenzoannulene (DBA) and tetrahedral tetra(4-
DBA-3D-COF 1 was synthesized under solvothermal condi-
tions by reacting DBA[12] with TBPM in a 10:1 (v/v) 1,4-
dioxane and mesitylene mixture in flame-sealed glass ampules
at 95°C for 3 days (Scheme 1). DBA-3D-COF 1 was obtained
by filtration and washed with acetonitrile in an argon-purged
31
dihydroxyborylphenyl)methane (TBPM) units. DBAs are pla-
nar triangular shaped macrocycles that are capable of forming
32
33
strong metal complexes with Li, and Ca, and low oxidation
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intense peaks at 2.88, 4.01, 4.92, 6.89, 7.97°, which corre-
(a)$(1#1#1)#
1
2
3
4
5
6
7
8
spond to the (100), (110), (111), (211), and (220) planes respec-
tively. The crystal structure of DBA-3D-COF 1 was simulated
using the Reflex module of the Materials Studio 7.0 software.
Pawley refinement of the experimental data using a bor net
provided unit cell parameters of a = b = c = 31.953 Å (residu-
als Rp= 6.44, Rwp= 9.70). The simulated PXRD profile was in
good agreement with the experimental data. We also consid-
ered the ctn net, but the simulated PXRD did not match the
experimental data (Figure S6, SI). In addition, DBA-3D-COF
(1#0#0)#
(1#1#0)#
9
(2#1#1)#
(2#2#0)#
-3
1 exhibits a density of 0.13 g cm , which is lower than the
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-3
reported densities of COF-102 (0.41 g cm ), COF-105 (0.18 g
-3
-3
cm ), and COF-108 (0.17 g cm ). The PXRD profile of Ni-
DBA-3D-COF revealed retention of crystallinity and preserva-
tion of the framework following metalation with Ni(COD)2
(Figure 1b). Interestingly, Fourier transform infrared (FT-IR)
spectroscopy revealed similar B-O stretching modes at 1340
5
10
15
20
25
30
2θ (Degrees)
O
O
O
O
(b)$
B
B
-1
O
O
and 1337 cm for DBA-3D-COF 1 and Ni-DBA-3D-COF,
B
B
O
O
O
O
respectively (Figures S1 & S2, SI). This suggests that the metal
is bound exclusively in the cavity of DBA[12] to produce a
B
O
B
O
B
O
B
O
O
O
37
Ni(0) complex with no interaction at the boronate ester link-
O
O
B
age. Inductively coupled plasma-atomic emission spectroscopy
(ICP-AES) analysis indicated that ~10.1 wt% of Ni was incor-
porated into Ni-DBA-3D-COF.
O
B
O
O
B
O
B
O
O
5
10
15
20
25
30
2θ (Degrees)
5
4
3
2
1
0
Figure 1. (a) Indexed experimental (red) and Pawley refined
(blue) PXRD patterns of DBA-3D-COF 1 compared to the bor
simulated unit cell (green) with views along the x and y direction
of the cubic crystal model. (b) PXRD of Ni-DBA-3D-COF with a
structure showing Ni(0) (purple circle) bound in the cavity of
DBA[12].
glove box to produce a light green crystalline powder. The
ideal reaction conditions were obtained by screening different
temperatures, monomer and solvent ratios, and reaction times.
(see pp. S10 in the Supporting information (SI)). It should be
noted that samples in which both DBA[12] and TBPM mon-
omers were fully soluble prior to sealing the ampules typically
yielded the best results. These homogeneous conditions are
consistent with what has been observed for obtaining the effi-
200
300
400
500
600
700
800
Wavelength+(nm)+
Figure 2. Kubelka-Munk diffuse reflectance spectra and photo-
graphs of DBA-3D-COF 1 (green) and Ni-DBA-3D-COF (pur-
ple).
36
cient growth of 2D COFs. Thermogravimetric analysis re-
vealed that DBA-3D-COF 1 maintains ~ 95% of it’s weight
up to 458°C (Figure S13, SI). Scanning electron microscopy
(SEM) images revealed the formation of rhombic shaped crys-
tallites (Figure S26, SI). Metalation was achieved by adding a
solution containing 10 wt% Ni(COD)2 dissolved in 1 mL of
dry toluene to ~34 mg of DBA-3D-COF 1. The mixture was
then stirred at room temperature in an argon-purged glove
box for 24 h to produce Ni-DBA-3D-COF as a dark purple
crystalline powder. Ni-DBA-3D-COF was obtained by filtra-
tion, washed with dry toluene to remove excess Ni(COD)2, and
dried under vacuum at 35°C for 16 h.
In order to confirm the presence of DBA-Ni(0) complex, we
also characterized DBA-3D-COF 1 and Ni-DBA-3D-COF
13
utilizing solid-state C cross-polarization magic angle spinning
(CP-MAS) NMR, UV-vis diffuse reflectance, and solid-state
fluorescence spectroscopies. The presence of the alkynyl units
13
for DBA-3D-COF 1 were confirmed by C CP-MAS NMR
exhibiting a distinct resonance at ~ 91 ppm (Figure S7, SI).
Upon metalation, the alkynyl peak of DBA-3D-COF 1 experi-
enced 15 ppm downfield shift from 91 to 106 ppm due to the
formation of a DBA-Ni(0) complex (Figure S8, SI.) These re-
The crystallinity of DBA-3D-COF 1 and Ni-DBA-3D-COF
were evaluated using powder X-ray diffraction (PXRD). Fig-
ure 1a shows the experimental and refined PXRD profile for
DBA-3D-COF 1. Since DBA-3D-COF 1 was constructed
utilizing tetrahedral and triangular shaped monomers, we pre-
dicted that combining both structures would yield a non-
interpenetrated 3D cubic lattice with a bor (P-43m) net topol-
13
sults are consistent with C NMR shifts that were previously
reported by Youngs and coworkers for a single molecule DBA-
37
Ni(0) complex. The UV-vis diffuse-reflectance spectrum of
DBA-3D-COF 1 exhibits a broad absorbance from 300 to 420
nm (Figure 2). After metalation, a new charge transfer absorp-
tion band emerges at ~ 575 nm for Ni-DBA-3D-COF, which
-
is indicative of three alkynyl units donating 2e to form the
24
ogy reminiscent of COF-108. DBA-3D-COF 1 exhibited
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Journal of the American Chemical Society
value of 3.1 nm. The total pore volume calculated at P/P0 =
1400
1200
1000
800
600
400
200
0
3
-1
1
2
3
4
5
6
7
8
0.974 afforded a value of 1.85 cm g . Surprisingly, Ni-DBA-
3D-COF also exhibited a type-IV isotherm. Application of the
BET model over the low-pressure 0.07 < P/P0 < 0.11 range
2
-1
provided a surface area of 4763 m g . The NLDFT pore size
of Ni-DBA-3D-COF experienced a slight 0.2 nm decrease to
provide an average pore size of 2.6 nm. The total pore volume
3
-1
calculated at P/P0 = 0.975 yielded a value of 1.59 cm g .
Since we believe Ni(0) is predominantly bound within the tri-
angular pore of the DBA[12] units, we believe that these slight
reductions are likely attributed to small a quantity of unbound
Ni(II) trapped within the pores of the material.
9
0
0.2
0.4
0.6
0.8
1
10
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12
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P/P0
3
2.5
2
__________________________________________________
2.6 nm
3.5
2.5
3
2.8 nm
273 K
273 K
2.5
2
2
1.5
1
1.5
1
1.5
1
295 K
295 K
0.5
0
0.5
0
0.5
0
0
0.2
0.4
0.6
0.8
1
1.2
0
0.2
0.4
0.6
0.8
1
1.2
Pressure (bar)
Pressure (bar)
0
1
2
3
4
5
6
Figure 4. Ethane (left) and ethylene (right) adsorp-
tion/desorption isotherms for DBA-3D-COF 1 (circle) and Ni-
DBA-3D-COF (square). All isotherms were measured at 273 K
(red) and 295 K (blue).
Pore Width (nm)
Figure 3. Nitrogen adsorption/desorption isotherms (top) and
NLDFT pore size distributions (bottom) for DBA-3D-COF 1 (red)
and Ni-DBA-3D-COF (blue) measured at 77 K.
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To determine if Ni-DBA-3D-COF could be effective at per-
forming ethane/ethylene separations, we measured gas ad-
sorption isotherms for both COFs at 273 and 295 K from 0 to
1.2 bar (Figure 4). DBA-3D-COF 1 exhibited swift uptake of
DBA-Ni(0) 16 electron complex. In addition, DBA-3D-COF 1
is highly luminescent in the solid-state exhibiting
λmax of 510 nm, which is blue-shifted by ~ 20 nm from the 2D
DBA-COFs
of DBA-3D-COF 1 is quenched after metalation further indi-
cating that the Ni(0) is being incorporated within the triangu-
lar pore of the DBA[12] units.
a
38,39
(Figure S27, SI). However, the luminescence
-1
ethane at low pressures reaching capacities of 3.24 mmol g at
-1
273 K and 2.09 mmol g at 295 K. The ethylene uptake ca-
-1
pacities were much lower reaching values of 2.52 mmol g at
-1
273 K and 1.70 mmol g at 295 K. In comparison, Ni-DBA-
X-ray photoelectron spectroscopy (XPS) analysis of
Ni(COD)2 and Ni-DBA-3D-COF revealed the presence of two
Ni species with different oxidation states (Figure S29, SI).
Ni(COD)2 displayed two broad peaks at 856.26 and 853.26
eV, which correspond to the core energy levels of Ni(II)2p3/2
and Ni(0) 2p3/2, respectively. In contrast, the energy level for
Ni(0) 2p3/2 shifts upfield by ~ 0.8 eV to 852.44 eV for Ni-
DBA-3D-COF indicating that the Ni(0) atoms are binding
with the alkynyl units of DBA[12]. The broad peak for the
Ni(II)2p3/2 energy level of Ni-DBA-3D-COF experienced a
small upfield shift of ~ 0.1 eV which suggests a weak binding
interaction with the alkynyl units. The presence of the boron,
carbon, and oxygen atoms of Ni-DBA-3D-COF were also
confirmed by XPS (Figure S28, SI).
-1
3D-COF displayed uptake capacities of 3.01 mmol g and
-1
-1
-
2.16 mmol g for ethane, and 2.36 mmol g and 1.83 mmol g
1
for ethylene at 273 and 295 K, respectively. Surprisingly, the
metalated Ni-DBA-3D-COF displayed only a modest increase
of 0.07 mmol for ethane, and 0.13 mmol for ethylene at 295
K. These slight increases are likely attributed to the ability of
40
the open Ni(0) sites to polarize ethane, and weak π -
complexation between the d-orbitals of Ni(0) and the π orbitals
41
of ethylene. The ethane/ethylene selectivities of DBA-3D-
COF 1 and Ni-DBA-3D-COF were calculated using initial
slope calculations in the pressure range of 0-0.1 bar to afford
values of 1.25 and 1.28 at 273 K, and 1.24 and 1.15 at 295 K,
respectively (Figures S16-S19, SI). The isosteric heats of ad-
sorption (Qst) were estimated using the virial method to assess
the binding affinity of ethane and ethylene to both materials.
The porosity of DBA-3D-COF 1 and Ni-DBA-3D-COF
were determined by nitrogen gas adsorption measurements at
77 K. DBA-3D-COF 1 exhibited a type-IV isotherm display-
ing a sharp uptake at low relative pressure (P/P0 < 0.1) fol-
lowed by a sharp step between P/P0 = 0.05 and 0.13 which is
indicative of a mesoporous material (Figure 3), The Brunauer-
Emmet-Teller (BET) model was applied over the low-pressure
region (0.07 < P/P0 < 0.11) of the isotherm to provide a sur-
-1
DBA-3D-COF 1 exhibited Qst values of 16.8 kJ mol for
-1
ethane and 15.9 kJ mol ethylene, while Ni-DBA-3D-COF
-1
-
displayed Qst values of 11.6 kJ mol for ethane and 9.7 kJ mol
1
for ethylene at 295 K, at zero coverage (Figures S20 & S21,
SI). These results indicate that the open metal sites of Ni-DBA-
3D-COF do not significantly enhance their binding interac-
tions with ethane or ethylene relative to DBA-3D-COF 1.
However, Ni-DBA-3D-COF could be useful as a neutral het-
2
-1
face area of 5083 m g . It should be noted that the BET sur-
42
2
erogeneous catalyst for ethylene polymerizations.
face area of DBA-3D-COF 1 is larger than COF-102 (3472 m
-1
2
-1 24
g ) and COF-103 (4210 m g ). The pore size distribution of
DBA-3D-COF 1, which was estimated using nonlocal density
functional theory (NLDFT), provided an average pore size of
2.8 nm. The experimental pore size is close to the predicted
In conclusion, we have demonstrated that a DBA[12] mon-
omer can be used to create a highly porous 3D COF that re-
tains its crystallinity upon metalation with Ni. Metalation of
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area and pore volume of the material. To the best of our
knowledge, this is the first example of metalating a 3D COF
with Ni. The proof-of-principle is important, as DBA mono-
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mers also have the ability to bind Li, Ca, and other low
34,35
oxidation state transition metals.
With this in mind, we
believe this work increases the prospect of using metalated
43
DBA-based COFs for applications related to catalysis, gas
19-21
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ASSOCIATED CONTENT
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Supporting Information
13
Synthetic procedures, FT-IR, solid-state C NMR, XPS,
TGA PXRD, and SEM. This material is available free of
charge via the internet at http://pubs.acs.org.
The Supporting Information is available free of charge on the
ACS Publications website.
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Corresponding Author
*mcgrier.1@osu.edu
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENTS
P.L.M acknowledges the National Science Foundation (NSF)
and Georgia Tech Facilitating Academic Careers in Engineer-
ing and Science (GT-FACES) for a Career Initiation Grant,
and funding from The American Chemical Society Petroleum
Research Fund (55562-DNI7), NSF (DMR-0114098), and
The Ohio State University.
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