A Strategic High Yield Synthesis of 2,5-Dihydroxy-1,4-benzoquinone Based MOFs

Article abstract of DOI:10.1021/acs.inorgchem.9b00903

Metal organic frameworks (MOFs) of the type NBu₄M(DHBQ)_1.5 (M = Ni²⁺, Fe²⁺, and Co²⁺ DHBQ = 2,5-dihydroxy-1,4-benzoquinone) were prepared with improved yield up to 100% via a simple benchtop aqueous addition reaction. For the first time, the crystalline phase of this formula polymer was synthesized without in situ generation of the DHBQ ligand from 2, 5-diamino-1,4-benzoquinone (DABQ). Powder X-ray diffraction and elemental analysis confirm the crystalline phase and composition of products. Infrared and electron dispersive spectroscopy further confirm that the materials are homologous to the reported single crystalline polymers. The present MOF synthesis can be extended to halide-substituted ligands, i.e., 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone (chloranilic acid, CAN) and 3,6-difluoro-2,5-dihydroxy-1,4-benzoquinone (fluoranilic acid, FAN).

Full text of DOI:10.1021/acs.inorgchem.9b00903

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
A Strategic High Yield Synthesis of 2,5-Dihydroxy-1,4-benzoquinone
Based MOFs
Kevin V. Nielson, Liping Zhang, Qiang Zhang, and T. Leo Liu*,†
†
†
‡
†
Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322, United States
‡
Department of Chemistry, Washington State University, Pullman, Washington 99163, United States
*
S Supporting Information
2
+
2+
2+
ABSTRACT: Metal organic frameworks (MOFs) of the type NBu M(DHBQ)1.5 (M = Ni , Fe , and Co ; DHBQ = 2,5-
4
dihydroxy-1,4-benzoquinone) were prepared with improved yield up to 100% via a simple benchtop aqueous addition reaction.
For the first time, the crystalline phase of this formula polymer was synthesized without in situ generation of the DHBQ ligand
from 2, 5-diamino-1,4-benzoquinone (DABQ). Powder X-ray diffraction and elemental analysis confirm the crystalline phase
and composition of products. Infrared and electron dispersive spectroscopy further confirm that the materials are homologous
to the reported single crystalline polymers. The present MOF synthesis can be extended to halide-substituted ligands, i.e., 3,6-
dichloro-2,5-dihydroxy-1,4-benzoquinone (chloranilic acid, CAN) and 3,6-difluoro-2,5-dihydroxy-1,4-benzoquinone (fluoranilic
acid, FAN).
INTRODUCTION
However, the synthesis of these materials is not straightfor-
ward. Both research groups and following publications
employed an indirect synthetic method whereby the DHBQ
ligand was not used in the synthesis in favor of 2,5-diamino-
■
1
−4
Electrically conductive metal organic frameworks (MOFs)
represent an important extension of the applications of MOF
materials beyond their current applications in gas sorption/
1
,4-benzoquinone (DABQ) which undergoes in situ hydrolysis
5
separation, sensors, and catalysis. Indeed, over the past ten
9
to become the DHBQ ligand (see Figure 1A and Scheme S1).
The reported reactions were typically done on a milligram
scale in sealed glass vial reactors above the boiling point of the
solvent. These conditions led to low yields (<43%), requiring
up to 48 h of reaction time. To further study these polymers or
produce them on a large enough scale for materials utilization,
a straightforward, high-yield synthesis needs to be demon-
strated. In addition, it is important to mention that for a scaled-
up synthesis of NBu M(DHBQ) crystalline polymers, the
years, conductive MOFs have found use in a variety of
applications including, but not limited to, electrocatalysis,
thermoelectrics, field effect transistors, and supercapaci-
4
,6−8
tors.
of single crystals for a family of coordination polymers with
formula NBu M(DHBQ) (M = Mn, Fe, Co, Ni, Zn, and
In 2011 Abrahams et al. reported on the synthesis
4
1.5
9
Cd). This pioneering research inspired others, including
Long’s research group, to more closely examine this family of
4
1.5
1
0−12
MOF polymers.
.5 by studying its electrical and magnetic properties.
Their results concluded that this material had a very high
Long’s group analyzed NBu Fe(DHBQ)-
direct use of the DHBQ ligand is intuitively desired rather than
DABQ. This is due in part to the much lower cost of DHBQ
compared to DABQ (see Table S1 for price comparison of
several major vendors). However, no study has been reported
4
10,11
1
electrical conductivity (10− S cm ) and high ferromagnetic
ordering temperature (130 K), making this a desirable material
for applications requiring high charge mobility. Recently, our
group has also become interested in this class of MOF
materials specifically to exploit their non-innocent DHBQ
ligand-based redox properties for energy storage/conversion
applications.
2
−1
on the direct use of this ligand in making NBu
MOF materials. Herein, we report the highly efficient, selective
M(DHBQ)1.5
4
synthesis of NBu M(DHBQ) MOFs (M = Ni and Fe) using
4
1.5
Received: March 29, 2019
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b00903
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Figure 1. (A) Literature reported NBu Ni(DHBQ) by in situ hydrolysis of DABQ to DHBQ. (B) Synthesis of NBu Ni(DHBQ) reported here
4
1.5
4
1.5
2
+
by direct use of the DHBQ ligand. (C) Generation of Ni(DHBQ)(H O) one-dimensional polymer by direct mixing Ni and DHBQ at room
2
2
temperature.
the DHBQ ligand under strategically controlled reaction
conditions.
some small crystals were observed above the solvent line. The solid
components were extracted by vacuum filtration with rinsing by
degassed water. The solids were dried in a vacuum oven at 100 °C for
1
h. Yield: < 20 mg, 47%. Anal. calcd for C H NiNO : C, 59.07; H,
25 39 6
EXPERIMENTAL SECTION
1
■
7.73; N, 2.75. Found: C, 55.01; H, 6.36; N, 5.54. H NMR (300
MHz, 4 drops conc. HCl in 1 mL of DMSO-d , TMS): δ 7.27 (acid),
5.63 (3H; aromatic CH), 2.88 (6.92 H; NBu CH ), 1.27 (6.91 H;
NBu CH ), 1.00 (6.90 H; NBu CH ), 0.61 (10.44 H; NBu CH
(see the XRD spectra in Figure S2).
Literature Synthesis of NBu
Chemicals and Instruments. All chemicals were purchased from
TCI, stored in an Ar glovebox, and used directly. Elemental analysis
was performed by Atlantic Microlabs. SEM was performed on a FEI
Quanta FEG 650. PXRD results were obtained from a Rigaku
MiniFlex II table-top X-ray diffractometer with a silicon wafer sample
holder. FT-IR was performed on a PerkinElmer Spectrum 100 FT-IR
spectrometer with a universal ATR sampling accessory. NMR analysis
was performed on a Jeol 300 MHz spectrometer. All reagents and
prepared samples were dried at 100 °C in a vacuum oven before
masses were taken.
6
4
2
)
3
4
2
4
2
4
Fe(DHBQ)1.5. The exact con-
ditions reported by Long et al. were utilized to prepare this sample.
The conditions were the same as the above synthesis for
4
7
NBu
mmol) was used in place of Ni(OAc)
Anal. calcd for C25 39FeNO : C, 59.41; H, 7.78; N, 2.77. Found: C,
55.14; H, 6.50; N, 5.58.
Ni(DHBQ)(H O) . The conditions reported by Abrahams and
Ni(DHBQ)1.5 except that Fe(SO
)
·7H
2
O (150.4 mg, 0.5409
O. Yield: < 15 mg, 63%.
4
4
2
2
·4H
2
H
6
SEM Sample Preparation. First, 1.0 mg of sample powder was
dispersed in 1.0 mL of new degassed absolute ethanol. The sample
was sonicated for 30 min. Under Ar atmosphere glovebox conditions
2
2
Long for the Ni and Fe polymers, respectively, were followed,
excepting the direct use of 2,5-dihydroxy-1,4-benzoquinone. Gray
(Ni) or Black (Fe) powders were collected by filtration. These
reactions did not produce the correct phase of material, so reporting a
percent yield is not meaningful. Additionally, it was found that low
crystallinity one-dimensional polymers formulated as M(DHBQ)-
(
< 1.0 ppm of O , < 0.1 ppm of H O), several drops of suspension
2
2
were layered onto an Al SEM sample stub and left to dry. The samples
were then sealed in air-free SEM sample holders for transportation.
The sample stubs were loaded into the FEI Quanta FEG 650 under a
cool stream of nitrogen and then tested under reduced pressures (<
5
5
.0 × 10− mm Hg).
(H
presence of NBu salts. Highly crystalline NiDHBQ(H O) could be
4 2 2
2
O) were generated at room temperature with or without the
+
Literature Synthesis of NBu Ni(DHBQ)1.5. The exact conditions
4
13
reported by Abrahams et al. were utilized to prepare this sample. In
brief, 2,5-diamino-1,4-hydroquinone dihydrochloride (38.14 mg,
prepared by combining aqueous metal solution to ligand solution at
100 °C, cooling the solution to room temperature, and rinsing it with
water and ethanol on the filter.
0
.1803 mmol) was dissolved in 30 mL of D.I. H O and bubbled
2
with oxygen to generate 2,5-diamino-1,4-benzoquine. The solution
was then cleared of oxygen by freeze pump thaw. Tetra butyl
ammonium bromide (excess, 300 mg) was dissolved, followed by
dissolution of Ni(OAc) ·4H O (44.86 mg, 0.1803 mmol). This
New Synthesis of NBu Ni(DHBQ)1.5. DHBQ (1.5 mmol, 210
4
mg) and NBu Br (excess, 2.0 g) were dissolved in 50 mL of degassed
4
H O under N reflux. Ni(OAc) ·4H O (248.84 mg, 1.0 mmol) was
2
2
2
2
dissolved separately in 10 mL of degassed H O, added dropwise over
2
2
2
suspension was loaded into a thick-walled glass vial and flame-sealed.
The vial was placed in a preheated 120 °C oven for 48 h and then
removed all at once. A black precipitate lined the walls of the vial, and
15 min, and then was left to reflux for an additional 30 min. A carrot-
orange precipitate was extracted by vacuum filtration and rinsing with
water. Yield: 510.0 mg, 100%. Anal. calcd for C H NiNO : C, 59.07;
2
5
39
6
B
DOI: 10.1021/acs.inorgchem.9b00903
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
1
H, 7.73; N, 2.75. Found: C, 58.92; H, 7.67; N, 2.73. H NMR (300
MHz, 4 drops HCl in 1 mL of DMSO-d , TMS): δ 6.93 (acid), 5.54
6
(
3H; aromatic CH), 2.73 (7.97 H; NBu CH ), 1.13 (7.99 H; NBu
4 2 4
CH ), 0.86 (7.98 H; NBu CH ), 0.47 (12.0 H; NBu CH ) (see the
2
4
2
4
3
NMR spectrum of acid digested NiBu Ni(DHBQ) in Figure S6).
4
New Synthesis of NBu Fe(DHBQ)1.5. The conditions were the
4
same as the previous synthesis with minor modifications. FeSO4·
7
H O (278 mg, 1.0 mmol) was used as the metal source, and a greater
2
excess of NBu Br (3.0−4.0 g) was found to improve the yield. Also,
4
air sensitivity was observed for this material by loss of crystallinity
after air exposure. As such, air-free Schlenck filtration under N was
2
utilized to extract a black-purple microcrystalline precipitate that was
then stored in an inert atmosphere. Yield: 434.6 mg, 86%. Anal. calcd
for C H FeNO : C, 59.41; H, 7.78; N, 2.77. Found: C, 59.95; H,
25
39
6
7
.86; N, 2.76.
Synthesis of NBu Ni(CAN)1.5. 3,6-Dichloro-2,5-dihydroxy-1,4-
4
benzoquinone (chloranilic acid, CAN) (0.3 mmol, 60.0 mg) and
NBu Br (1.0 mmol, 322 mg) were dissolved in 100 mL of degassed
4
H O under N reflux. Ni(NO ) ·6H O (58.0 mg, 0.2 mmol) was
2
2
3
2
2
dissolved separately in 10 mL of degassed H O, added dropwise over
2
1
5 min, and then was left to reflux for an additional 30 min. A brown
precipitate was extracted by vacuum filtration and rinsing with water.
Yield: 175.0 mg, 96.4%. Anal. calcd for C H FNiNO Cl : C, 49.0;
2
5
36
6
3
H, 5.88; N, 2.29; Cl, 17.39. Found: C, 49.95; H, 6.71; N, 2.40; Cl,
1
6.76. PXRD results can be seen in Figure S4.
Synthesis of NBu Ni(FAN)1.5. 3,6-Difluoro-2,5-dihydroxy-1,4-
4
benzoquinone (fluoranilic acid, FAN) (0.3 mmol, 53.4 mg) and
NBu Br (1.0 mmol, 322 mg) were dissolved in 100 mL of degassed
4
H O under N reflux. Ni(NO ) ·6H O (58.0 mg, 0.2 mmol) was
2
2
3
2
2
dissolved separately in 10 mL of degassed H O, added dropwise over
2
1
5 min, and then was left to reflux for an additional 30 min. A brown
Figure 2. X-ray diffraction data obtained from samples prepared by
facile synthesis compared to simulated patterns for (A) Ni(DHBQ)-
precipitate was extracted by vacuum filtration and rinsing with water.
Yield: 120.0 mg, 96.2%. Anal. calcd for C H FNiNO F : C, 53.40;
H, 6.45; N, 2.49; F, 10.13. Found: C, 53.66; H, 6.76; N, 2.50; F, 9.75.
PXRD results can be seen in Figure S5.
2
5
36
6 3
(
H O) prepared by room temperature reagent combination. Hot
2 2
addition reactions presented for (B) NBu Ni(DHBQ) and (C)
4
1.5
NBu Fe(DHBQ) .
4
1.5
RESULTS AND DISCUSSION
■
lower than the formula ratio (3:8), 1.5:1, further suggesting the
present of the NH4+ cation.
To prepare the as-mentioned MOFs, first, the exact synthetic
procedures were followed from Abrahams et al. for the
NBu Ni(DHBQ) MOFs using Ni(OAc) ·4H O and DABQ
Initial attempts to synthesize NBu Ni(DHBQ) followed
4
1.5
4
1.5
2
2
the synthetic method reported by Abrahams exactly, excepting
the direct use of DHBQ over 2,5-amino-p-quinone. However,
it was observed every time that the metal and ligand, with or
in the presence of excess NBu Br. The X-ray diffraction pattern
4
obtained was in close agreement to the simulated pattern
obtained from the reported NBu Ni(DHBQ) MOF crystal
4
1.5
without the NBu Br salt, was combined, precipitates
+
4
structure where the NBu4 cation was squeezed because of
immediately began to fall out of solution at room temperature.
9
disorder. The location of all peaks was a good match,
There was no indication of the correct phase of material by
confirming the presence of the reported crystalline phase for
13,14
PXRD (Figure 2A). According to the literature,
the
NBu Ni(DHBQ) (Figure 2). The relative intensities of some
4
1.5
obtained PXRD pattern indicates only the formation of the
one-dimensional polymer, Ni(DHBQ)(H O) . Even after
peaks are not in close agreement, which is explained as there is
2
2
+
1
no NBu4 cation in the simulated PXRD pattern. In the H
heating at 120 °C for 2 days, the linear polymer diffraction
1
NMR spectrum of H NMR studies of HCl-digested MOF
pattern was still observed without the formation of NBu Ni-
4
samples (Figure S7), the proton resonances for the in-situ
formed DHBQ from the hydrolysis of DABQ and the Bu N
(
DHBQ) . In the case of Fe, only amorphous or unknown
1.5
n
+
4
phases could be observed by PXRD under the same conditions.
The precipitation of the linear polymer Ni(DHBQ)(H O)
cation were confirmed. The elemental analysis performed on
these samples indicated a 2-fold excess of nitrogen for both
samples, suggesting incomplete hydrolysis of the amine or
2
2
dominated the reaction chemistry when Ni(OAc) ·4H O,
2
2
tetrabutylammonium salts, and DHBQ were directly mixed at
room temperature. This phenomenon was attributed to the
low solubility (<3 mM) of DHBQ in water at ambient
temperatures and high solubility of the metal salt. We
envisioned that slow addition of the Ni salt into a refluxing
aqueous solution of DHBQ (20 mM) would instead maintain a
high ligand-to-metal ratio and favor the desired three-ligand-
coordinated NBu Ni(DHBQ) over the two-ligand-coordi-
+
incorporation of NH4 cations into the product. The presence
+
of NH4 in the product can be explained by the in-situ
hydrolysis of DABQ to produce NH and subsequent solvation
3
+
4
to NH OH (Scheme S1). It is reasonable to believe that NH
4
can be incorporated as counter cations into the Ni-MOF.
+
NH4 in the product is also corroborated by low C and H
1
percentages from elemental analysis (Scheme S1). In the H
4
1.5
NMR studies of the acid-digested MOFs (Figure S7), the
observed ratio (3:7) of the aromatic protons in DHBQ versus
nated linear polymer. We believe NBu Ni(DHBQ) is a
thermodynamic product formed at the reflux temperature,
4 1.5
n
+
the protons of one methylene group in the Bu N cation is
while the formation of the Ni(DHBQ)(H O) is kinetically
4
2
2
C
DOI: 10.1021/acs.inorgchem.9b00903
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Figure 3. SEM and EDS analysis of NBu Ni(DHBQ) (left) and NBu Fe(DHBQ) (right).
4
1.5
4
1.5
driven by precipitation at a lower temperature. By refluxing 50
mL of degassed water with the oil bath temperature set to 120
made by Long and co-workers concerning the increased CO
SEM
10,11
bond length in the DHBQ (3-) radical ligands.
°
C, we dissolved DHBQ and excess NBu Br. Ni(OAc) ·4H O
indicated uniform morphology for both samples (Figure 3).
The Ni MOFs appeared to lack a noticeable micrometer-sized
morphology; instead, they appear to be polycrystalline
nanoparticles. This observation is consistent with the broader
Bragg diffraction peaks (full width at half maximum at 18.84°;
2θ: c.a. 0.42°; 2θ: c.a. 20.2 nm) when compared to the
simulated spectra (Figure 2). The Fe polymer had a similar
morphology of submicrometer nanoparticle aggregates (full
width at half maximum at 18.84°; 2θ: c.a 0.40°; 2θ: c.a. 21.02
nm).
4
2
2
dissolved in H O was added dropwise with vigorous stirring
2
over 20−30 min while making sure that the water was boiling
before subsequent drops were added. After the metal solution
was added, the reaction was kept under reflux for an additional
3
0 min. The vial was removed from the oil bath and left until
the boiling dissipated. The contents of the flask were then
filtered hot using an air-free Schlenck filtration device under
Ar. The carrot-orange powder was then rinsed with degassed
H O and dried on the filter. The PXRD pattern of the
synthesized NBu Ni(DHBQ) MOFs matched the reported
phase (Figure 2B). The Ni sample remained stable after several
days exposed to ambient atmospheric conditions and showed
no loss of crystallinity by PXRD analysis. To further confirm
the generality of the synthesis route using the DHBQ ligand,
NBu Fe(DHBQ) was also prepared as purple (Fe) powders
2
We also conducted another reaction using Co(OAc) ·4H O
2
2
4
1.5
and observed the formation of the NBu Co(DHBQ) phase
4
1.5
by PXRD analysis (Figure S3). Moreover, the scope and
modularity of this synthetic method was briefly extended
further, beyond the DHBQ ligand, by substitution of 3,6-
dichloro-2,5-dihydroxy-1,4-benzoquinone (chloranilic acid,
CAN) and 3,6-difluoro-2,5-dihydroxy-1,4-benzoquinone (fluo-
ranilic acid, FAN) as bridging ligands. Under more dilute
4
1.5
using Fe(SO ) ·7H O, which was confirmed by the match of
4
2
2
the experimental and simulated PXRD results (Figure 2C).
The Fe sample, on the other hand, was highly sensitive to the
atmosphere and lost its crystallinity within 3 h of ambience.
Thus, it is very important to utilize air-free conditions when
handling the Fe MOFs.
conditions, NBu Ni(CAN)
and NBu Ni(FAN)
were
4
1.5
4
1.5
prepared as brown powders with PXRD spectra matching
9
,12
their simulated PXRD patterns (Figures S4 and S5).
Small
impurity peaks observed in the PXRD spectra of NBu Ni-
4
(
(
CAN)1.5 are likely attributed to a small unknown impurity
97%) in the chloroanilic acid reagent.
The elemental analysis for the Ni and Fe MOF samples
agreed quite well with their chemical formula. Indeed, by direct
use of DHBQ, the possibility of incomplete hydrolysis of
+
DABQ or NH incorporation is eliminated (Scheme S1). The
CONCLUSIONS
4
■
1
H NMR studies of acid-digested Ni-MOF samples consis-
In summary, NBu MDHBQ (M = Fe, Ni, Co) crystalline
4
1.5
tently determine the organic composition (Figure S6).
powders were prepared via a simple addition reaction of a
metal to ligand in boiling water. Via temperature regulation of
addition, the products were uniform and pure according to
+
Qualitatively, only DHBQ molecules and NBu4 cations were
observed for all samples digested by concentrated HCl. The
integration ratio (ca. 3:7.98) of peaks of the aromatic protons
in the DHBQ versus the protons of one methylene group in
1
XRD, FT-IR, SEM, EDS, H NMR, and EA analyses. Most
importantly, the straightforward synthesis utilizing the DHBQ
ligand rather than in situ generation of DHBQ was
demonstrated with a greater than 10-fold scale up of product
with improved yield up to 100% and with better elemental and
PXRD agreement than that produced by the sealed glass vial
reactor using DABQ. This synthesis was successfully
demonstrated for Ni, Fe, and Co and can reasonably be
extended to other divalent metals. By substituting chloranilate
or fluoranilate ligands for the DHBQ-based Ni-MOFs,
materials matching simulated PXRD were prepared. The
present convenience of DHBQ ligand-based (and its
n
+
the Bu N cation of the sample (Figure S6) prepared by the
4
slow addition method agreed better with the expected
chemical formula of NBu Ni(DHBQ) (3:8) than did the
4
1.5
integrations for the sample prepared by the hydrothermal
method (Figure S7).
The IR spectra of the Ni and Fe MOFs agreed with the
10,11
results reported in the literature (Figure S1).
Most notably
from the IR spectra, it was observed that the CO stretching
frequency for the Fe polymer was located 30 cm− lower than
the Ni polymer. This result is consistent with the conclusion
1
D
DOI: 10.1021/acs.inorgchem.9b00903
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
derivatives) MOFs will further promote their applications, such
as conductive MOFs and magnetic materials. Currently
investigations into MOF syntheses extending to other metals,
ligands, and ions are under way while exploiting the redox
chemistry of NBu M DHBQ (M = Fe and Ni) for potential
anilic Acid with the (10,3)-a Topology. Cryst. Growth Des. 2011, 11,
2
(
717−2720.
10) Darago, L. E.; Aubrey, M. L.; Yu, C. J.; Gonzalez, M. I.; Long, J.
R. Electronic Conductivity, Ferrimagnetic Ordering, and Reductive
Insertion Mediated by Organic Mixed-Valence in a Ferric Semi-
quinoid Metal−Organic Framework. J. Am. Chem. Soc. 2015, 137,
4
2
3
energy storage applications.
1
(
5703−15711.
11) Ziebel, M. E.; Darago, L. E.; Long, J. R. Control of Electronic
ASSOCIATED CONTENT
Supporting Information
Structure and Conductivity in Two-Dimensional Metal−Semiquinoid
Frameworks of Titanium, Vanadium, and Chromium. J. Am. Chem.
Soc. 2018, 140, 3040−3051.
■
*
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b00903.
(12) Murase, R.; Abrahams, B. F.; D’Alessandro, D. M.; Davies, C.
G.; Hudson, T. A.; Jameson, G. N. L.; Moubaraki, B.; Murray, K. S.;
Robson, R.; Sutton, A. L. Mixed Valency in a 3D Semiconducting
Iron-Fluoranilate Coordination Polymer. Inorg. Chem. 2017, 56,
Reaction schemes, FT-IR results, additional PXRD
results, NMR results of digested samples, and price
comparison of starting reagents (PDF)
9
(
025−9035.
13) Abrahams, B. F.; Dharma, A. D.; Dyett, B.; Hudson, T. A.;
Maynard-Casely, H.; Kingsbury, C. J.; McCormick, L. J.; Robson, R.;
Sutton, A. L.; White, K. F. An indirect generation of 1D MII-2,5-
dihydroxybenzoquinone coordination polymers, their structural
rearrangements and generation of materials with a high affinity for
H2, CO2 and CH4. Dalton Trans. 2016, 45, 1339−1344.
AUTHOR INFORMATION
Corresponding Author
E-mail: leo.liu@usu.edu.
■
*
(
14) Morikawa, S.; Yamada, T.; Kitagawa, H. Crystal Structure and
Proton Conductivity of a One-dimensional Coordination Polymer,
Mn(DHBQ)(H2O)2}. Chem. Lett. 2009, 38, 654−655.
ORCID
{
Qiang Zhang: 0000-0001-7327-9047
T. Leo Liu: 0000-0002-3698-1096
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank Utah State University for providing faculty startup
funds to the PI (T.L.L.) and the Utah Energy Triangle Faculty
Award sponsored by Utah State Governor’s Office of Energy
Development for supporting this study. Q.Z. acknowledges the
funding support by Washington State University.
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