Manganese-based layered coordination polymer: Synthesis, structural characterization, magnetic property, and electrochemical performance in lithium-ion batteries

Article abstract of DOI:10.1021/ic301579g

Manganese-based layered coordination polymer ([Mn(tfbdc)(4,4′-bpy) (H₂O)₂], Mn-LCP) with microporous structure was synthesized by reaction of 2,3,5,6-tetrafluoroterephthalatic acid(H ₂tfbdc) and 4,4′-bipyridine(4,4′-bpy) with manganese(II) acetate tetrahydrate in water solution. Mn-LCP was characterized by elemental analysis, IR spectra, thermogravimetric analysis, X-ray single-crystal structure analysis, and powder X-ray diffraction. Magnetic susceptibility data from 300 to 1.8K show that there is a weak antiferromagnetic exchange between Mn(II) ions in Mn-LCP. As anode material, the Mn-LCP electrode exhibits an irreversible high capacity in the first discharge process and a reversible lithium storage capacity of up to about 390 mA h/g from the fourth cycle. It might provide a new method for finding new electrode materials in lithium-ion batteries

Full text of DOI:10.1021/ic301579g

Article
pubs.acs.org/IC
Manganese-Based Layered Coordination Polymer: Synthesis,
Structural Characterization, Magnetic Property, and Electrochemical
Performance in Lithium-Ion Batteries
Qi Liu,*,†,‡ Lili Yu,‡ Ying Wang,† Yunzhou Ji,‡ Josip Horvat,§ Mei-Ling Cheng,‡ Xiaoyan Jia,‡
and Guoxiu Wang*,†
†Centre for Clean Energy Technology, School of Chemistry and Forensic Science, University of Technology Sydney, Broadway,
Sydney, New South Wales 2007, Australia
‡School of Petrochemical Engineering, Changzhou University, Changzhou 213164, P. R. China
§Institute for Superconducting and Electronic Materials, University of Wollongong, New South Wales 2522, Australia
S
* Supporting Information
ABSTRACT: Manganese-based layered coordination polymer ([Mn-
(tfbdc)(4,4′-bpy)(H2O)2], Mn−LCP) with microporous structure was
synthesized by reaction of 2,3,5,6-tetrafluoroterephthalatic acid(H2tfbdc)
and 4,4′-bipyridine(4,4′-bpy) with manganese(II) acetate tetrahydrate in
water solution. Mn−LCP was characterized by elemental analysis, IR
spectra, thermogravimetric analysis, X-ray single-crystal structure analysis,
and powder X-ray diffraction. Magnetic susceptibility data from 300 to
1.8K show that there is a weak antiferromagnetic exchange between
Mn(II) ions in Mn−LCP. As anode material, the Mn−LCP electrode
exhibits an irreversible high capacity in the first discharge process and a
reversible lithium storage capacity of up to about 390 mA h/g from the
fourth cycle. It might provide a new method for finding new electrode
materials in lithium-ion batteries
manganese carboxylate complexes along with their interesting
magnetic properties20 and the interesting hydrogen storage
properties of porous MOFs containing exposed fluorine
atoms,21 we continue to investigate materials with tetrafluor-
oterephthalate (tfbdc) and extend this work to the system of
Mn(II), H2tfbdc, and 4,4′-bipyridine (4,4′-bpy). The 4,4′-bpy
ligand has been extensively used in synthesizing one-dimen-
sional to three-dimensional coordination polymers with
catalytic, magnetic, unusual nonlinear optical, and conductive
properties.2,6b,22,23
1. INTRODUCTION
In recent years, metal−organic frameworks (MOFs) or
coordination polymers with porous structures have received
considerable attention for their unique physical and chemical
properties and many potential applications.1,2 Self-assembly of
metal-ion and/or metal clusters with varieties of organic linkers
has not only led to a unique type of porous materials for gas
storage,3,4 selective separation,5 catalysis,6 and drug delivery7
but also produced a series of functional materials with special
magnetic, nonlinear optical, and luminescent properties.8−10 In
particular, multibenzenecarboxylate ligands have been shown to
be good building blocks in the design of metal−organic
materials with desired topologies owing to their rich
coordination modes. One of the most frequently used linker
ligands is the dianion of terephthalic acid (H2bdc), from which
two of the most prominent members of this class of
compounds, MOF-511 and MIL-53,12 are constructed. The
perfluorinated terephthalic acid, that is, 2,3,5,6-tetrafluoroter-
ephthalic acid (H2tfbdc), is also a versatile building block for
construction of metal−organic complexes through complete or
partial deprotonation of its carboxyl groups, and some
interesting structures have been successfully obtained.13−17
Recently, we obtained several complexes with 2,3,5,6-
tetrafluoroterephthalate via self-assembly of H2tfbdc with
transition metal ions under mild solution synthetic con-
ditions.18,19 Considering the special bioactive function of
On the other hand, in order to improve the energy density
and thermal stability of lithium-ion batteries, many new
inorganic-based and organic-based electrode materials have
been synthesized.24,25 There have also been a few reports on
the electrochemical performance of three-dimensional (3D)
microporous metal−organic frameworks in lithium-ion bat-
́
teries.26−29 For example, G. Ferey et al.26 reported that MIL-
53(Fe) or FeIII(OH)0.8F0.2[O2C−C6H4−CO2] shows a rever-
sible electrochemical Li insertion with a very good cycling life
as a cathode material in lithium cells. It is a pity that its capacity
(70 mAh/g) is far lower than that of the commonly used
LiCoO2. On the basis of the facts that LiCoO2 cathode material
and carbon anode material have all layered structures, MOFs or
Received: July 20, 2012
Published: March 5, 2013
© 2013 American Chemical Society
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Crystallographic data for structural analyses are summarized in Table
1.
coordination polymers with two-dimensional (2D) layered
structures can also be candidates as electrode materials for
lithium-ion cells, considering that from the viewpoint of
material structure the metal cations with variable valence can
be active sites of redox reactions.26,30 However, to the best of
our knowledge, to date there have been few reports on the
electrochemical performance of 2D layered coordination
polymers in lithium batteries.31 Herein, we report the synthesis,
crystal structure, and magnetic property of a 2D manganese-
based coordination polymer ([Mn(tfbdc)(4,4′-bpy)(H2O)2],
Mn−LCP) and the electrochemical performance of it as an
anode material for lithium-ion batteries.
Table 1. Crystal Structure Parameters of Mn−LCP
formula
C18H12F4MnN2O6
calcd density/
1.740
(g·cm−3
)
fw
483.24
Mu(Mo Kα)/
0.797
mm−1
cryst
size/
mm
0.24 × 0.26 × 0.30 index ranges
(h, k, l)
−8/8, −9/9, −10/10
cryst syst triclinic
space Pi
group
F(000)
243
no. of reflns
collected
4138
̅
a/Å
7.136(1)
no. of
independent
reflns
1807 (Rint = 0.0492)
2. EXPERIMENTAL SECTION
2.1. Materials. 2,3,5,6-Tetrafluoroterephthalatic acid (H2tfbdc),
manganese(II) acetate tetrahydrate, 4,4′-bipyridine (4,4′-bpy), and
solvents were of reagent grade without further purification before use.
2.2. Synthesis of [Mn(tfbdc)(4,4′-bpy)(H2O)2]. A 5 mL amount
of a deionized water solution of Mn(OAc)2·4H2O (0.0245g, 0.10
mmol) was slowly added to 5 mL of a deionized water solution that
contained H2tfbdc (0.0238 g, 0.10 mmol) and 4,4′-bpy (0.0078 g, 0.05
mmol) to afford a colorless solution. Upon slow evaporation of the
solvent at room temperature for several days, colorless block crystals of
[Mn(tfbdc)(4,4′-bpy)(H2O)2](Mn-LCP) were obtained. Anal. Calcd
for C18H12F4MnN2O6: C, 44.74; H, 2.50; N, 5.80. Found: C, 44.70; H,
2.55; N, 5.76. IR data (cm−1, KBr pellet): 3460 (s), 3205 (w), 1605
(vs), 1535(m), 1492(w), 1469 (s), 1414 (w), 1386(vs), 1254 (w),
1218(m), 1131(w), 1068 (m), 1044(m), 1006(w), 982 (s), 806 (s),
733 (s), 686 (s), 648(w), 629 (s), 474 (s).
b/Å
c/Å
8.079(3)
8.522(2)
no. of obsd
reflns
1278
data/
restraints/
params
1807/0/ 142
α/deg
β/deg
γ/deg
90.55(2)
109.29(1)
95.35(2)
461.3(2)
goodness of fit
on F2
0.956
R1, wR2 [I >
2σ(I)]
0.0609, 0.1183
0.0807, 0.1243
0.511 and −0.277
R1, wR2 (all
data)
3
V/Å
largest diff.
peak and −3
hole/e·Å
Z
1
2.2. Physical Measurements. Elemental analysis (C, H, and N)
was performed on a Perkin-Elmer 2400 Series II element analyzer.
FTIR spectra were recorded on a Nicolet 460 spectrophotometer in
the form of KBr pellets. Thermogravimetric analysis (TGA)
experiments were carried out on a Dupont thermal analyzer from
room temperature to 800 °C under N2 atmosphere at a heating rate of
10 °C/min. The X-ray photoelectron spectrum of Mn−LCP was taken
on an ESCALAB MK II X-ray photoelectron spectrometer using a
nonmonochromatized Mg Kα X-ray as the excitation source and
choosing C1s (284.6 eV) as the reference line. Magnetic measure-
ments of the samples were performed on a SQUID magnetometer.
2.3. Electrochemical Measurement. For electrochemical testing,
Mn−LCP was dried for about 6 h at 50 °C in the vacuum oven prior
to being opened in an argon atmosphere. Electrodes were prepared
mixing crystalline Mn−LCP (80 wt %) with 10 wt % carbon black
(Super P, MMM, Belgium) and 10 wt % polyvinylidene fluoride
binder in N-methyl-2-pyrrolidinone solvent to form a homogeneous
slurry. Then, the slurry was spread onto a copper foil. Coated
electrodes were dried in a vacuum oven at 80 °C for 12 h and then
pressed. Electrochemical measurements were carried out using coin-
type cells. CR 2032 coin-type cells were assembled in an argon-filled
glovebox (Mbraun, Unilab, Germany) by stacking a porous
polypropylene separator containing liquid electrolyte between the
composite electrodes and a lithium-foil counter electrode. Electrolyte
used was 1 M LiPF6 in a 50:50 (v/v) mixture of ethylene carbonate
and dimethyl carbonate obtained from MERCK KgaA, Germany. Cells
were galvanostatically charged and discharged in the range of 0.01−2.5
V at a constant current density of 50 mAg−1.
3. RESULTS AND DISCUSSION
3.1. Crystal Structure Description of [Mn(tfbdc)(4,4′-
bpy)(H2O)2]. As shown in Figure 1, the Mn(II) ion has an
octahedral geometry coordinated by two O atoms from two
tfbdc dianions, two O atoms from two waters, and two N atoms
from two 4,4′-bpy molecules. N(1C), O(2), N(1), and O(2C)
atoms are in the equatorial position [Mn(1)−N(1C) =
2.309(3) Å, Mn(1)−O(2C) = 2.185(3) Å ]; O(3C) and
O(3) atoms are in the axial position [Mn(1)−O(3) =2.251(3)
2.4. X-ray Crystallography. Single-crystal X-ray diffraction
measurement of Mn−LCP was carried out with a Bruker Smart
Apex CCD diffractometer at 291(2) K. Intensities of reflections were
measured using graphite-monochromatized Mo Kα radiation (λ =
0.071073 nm) with the ψ−ω scans mode in the range of 2.53° ≤ θ ≤
25.99°. The structure was solved by direct methods using the
SHELXTL-9732computer program and refined by full-matrix least-
squares methods on F2 with the SHELXTL-97 program package.
Anisotropic thermal factors were assigned to all non-hydrogen atoms.
Hydrogen atoms were included in calculated positions and refined
with isotropic thermal parameters riding on the parent atoms.
Figure 1. Structure unit of [Mn(tfbdc)(4,4′-bpy)(H2O)2] (hydrogen
atoms omitted for clarity).
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Å]. The average bond length of Mn−N (0.2309 nm) is longer
than that of Mn−O (2.218 Å). The bond angles of O(3)−
Mn(1)−O(3C), N(1)−Mn1−N(1C), and O(2)−Mn(1)−
O(2C) are all 180.00°, further indicating the Mn(II) ion has
octahedral geometry. Each 4,4′-bpy and tfbdc dianion bridges
two Mn(II) ions to form a 2D microporous layer with (4,4)
topological network, as shown in Figure 2. The shortest
Figure 4. Powder X-ray diffraction pattern of the as-synthesized Mn−
LCP (A) and Mn−LCP after being vacuum dried at 50 °C for 6 h (B).
3.3. Infrared Spectrum. The IR spectrum of Mn−LCP
reflects the binding patterns of 4,4′-bpy, H2O, and 2,3,5,6-
tetrafluoroterephthalate (tfbdc). The strong absorption band in
the 3600−3200 cm−1 region corresponds to ν(OH) of the
coordination water molecules. All carboxylic groups are
deprotonated, as indicated by no absorption around 1730
cm−1 for a protonated carboxylic group. Strong peaks at 1605
and 1386 cm−1 are the νas(OCO) and νs(OCO) stretching
modes of coordinated tfbdc, respectively, while strong
absorption at ca. 733 cm−1 is the δ(OCO) bent vibration of
tfbdc.19 The difference of 219 cm−1 between νas(OCO) and
νs(OCO) indicates that the tfbdc ligands adopt an
amphimonodentate coordination mode34−36 as proved by X-
ray crystal structure analysis of Mn−LCP. The absorption
bands at ca. 3205 and 806 cm−1 are ν(C−H) stretching and
bent vibrations of 4,4′-bipy, respectively.37 The IR spectrum of
vacuum-dried Mn−LCP at 50 °C is the same as that of the as-
synthesized Mn−LCP, which indicates that such a vacuum-
drying step cannot sufficiently remove the coordinated water
molecules of the compound due to the stable nature of the
compound below 182 °C (Supporting Information Figure S2).
3.4. Magnetic Property. The temperature dependence of
the magnetic susceptibility of Mn−LCP was measured from 2
to 300 K with a Quantum Design SQUID magnetometer in an
applied magnetic field of 2000 Oe; data are shown in Figure 5
Figure 2. Two-dimensional layer structure of Mn−LCP.
distance Mn(II)−Mn(II) in the same layer is 11.686 Å. The 2D
structure of Mn−LCP is quite similar to that of [M(NDA)-
(4,4′-bpy)(H2O)2]·nH2O and [Mn(o-phth) 4,4′-bpy)(H2O)2]n
reported previously.33 Hydrogen-bonding interactions between
the layers [O3−H3A---F2 = 3.252(4) Å, O3−H3C---O1=
2.753(4) Å, and C1−H1---O2 = 3.192(4) Å] leads to formation
of a 3D network with tunnels as shown in Figure 3.
−1
as plots of χMT and χM versus T. The χMT product is 4.386
emu K mol−1 at 300 K, which is close to the value expected for
the spin-only value of the Mn(II) ion (4.376 emu K mol−1 with
Figure 3. Packing diagram of Mn−LCP viewed along the b axis;
dashed lines indicate there are hydrogen bonds between the layers.
Figure 4 shows the powder X-ray diffraction (XRD) pattern
of as-synthesized Mn−LCP and vacuum-dried Mn−LCP at 50
°C for 6 h. X-ray powder diffraction peak positions for vacuum-
dried Mn−LCP are the same as those of Mn−LCP, showing it
does not lose coordination water molecules and retains the
same structure of Mn−LCP.
3.2. Thermal Stability. TGA for Mn−LCP shows that
weight loss begins at 182 °C, indicating the framework of Mn−
LCP is stable at 182 °C. Weight loss from 182 to 249 °C
corresponds to two coordinated water molecules removed per
formula unit (calcd 7.46%, found 7.01%), and another weight
loss between 249 and 348.6 °C is ascribed to 4,4′-bpy molecule
removal (calcd 32.32%, found 35.97%) (see Supporting
Information Figure S1).
−1
■
○
Figure 5. Temperature dependence of χMT ( ) and χM ( ) for
Mn−LCP.
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g = 2.0). The χmT value decreases gradually on cooling, and a
value of 3.639 emu K mol−1 is reached at 2 K. Data can be fitted
nicely to the Curie−Weiss law, yielding C = 4.4 emu K mol−1
and Θ = −0.74 K. The results show the occurrence of very
weak antiferromagnetic interactions between the Mn(II)
centers in Mn−LCP.
maintains a capacity of about 390 mAh/g, indicating good
cycling stability of the Mn−LCP electrode.
To learn about the electrochemical reactions in the Mn−
LCP electrode, we examined FTIR spectra of the Mn−LCP
electrodes and electrolyte; the results are shown in Figure 7.
3.5. Electrochemical Performance for Lithium Stor-
age. The electrochemical performance of Mn−LCP for lithium
storage in lithium-ion cells was investigated by cyclic
voltammetry (CV) and a galvanostatic charge/discharge cycling
test. Figure 6a shows the CV curves of the Mn−LCP electrode
Figure 7. FTIR spectra of the Mn−LCP (a) bare electrode, (b)
discharge at 0.01 V, (c) charge at 2.5 V, and (d) electrolyte containing
ethylene carbonate (EC), dimethyl carbonate (DMC), and LiPF6.
The fact that the characteristic peak of the carboxylate group
from the tfbdc anion at 1605 cm−1 appears in FTIR spectra of
the bare electrode, the discharged and charged electrodes,
shows the tfbdc anions are reversibly involved in the cycling.
For confirming changes in the oxidation state of manganese
under discharge and charge states, magnetic measurements of
used and unused electrodes were carried out. As shown in
Figure 8, after the first discharge to 0.01 V, the magnetic
Figure 6. (a) CV curves of the Mn−LCP electrode. (b) Charge/
discharge profiles of the Mn−LCP electrode in a lithium-ion cell.
(Inset) Discharge capacity vs cycle number from the second cycle.
in the voltage range of 0.1−3.0 V. The cathodic peak at around
0.45 V should correspond to [Li2(tfbdc)(4,4′-bpy)] formation
during the first discharge (eq 1 below).
Figure 8. Temperature dependence of magnetic susceptibility (χ) for
The peak at around 0.45 V disappears after the first
discharge, leaving an initial irreversible capacity, as shown in
Figure 6b. The cathodic peaks at around 0.1 and 0.7 V during
discharging and the broad anodic peak at 0.75−1.4 V during the
charging process, which may be assigned to the reduction and
oxidation peaks of the Mn(II)/Mn pair, will be mentioned later.
Figure 6b shows the charge/discharge profiles of the Mn−LCP
electrode. The cycling performance (reversible lithium storage
vs cycle number) is shown as the inset in Figure 6b. The first
discharge capacity of the Mn−LCP electrode is 1807 mAh/g,
but the second discharge capacity is only 552 mA h/g.
Compared with the capacity of the first and second cycles,
capacity loss is as high as 69.5%. However, from the fourth
cycle, the Mn−LCP electrode demonstrates a stable capacity
for reversible lithium storage. After 50 cycles, the electrode
■
selected samples: pristine electrode prepared with Mn−LCP ( ), 0.01
○
V ( ), and 2.5 V (Δ).
susceptibility value (χ100K = 2.681 × 10−5 emu g−1) of electrode
materials is lower than that of the pristine electrode materials
consisting of Mn−LCP, carbon black, and binder additives
(χ100K = 7.640 × 10−5 emu g−1), which agrees with loss of Mn2+
and occurrence of Mn0; a similar change has been observed in
the MnCO3 electrode.38 After battery recharge to 2.5 V, the
magnetic susceptibility value of electrode materials at 100 K is
different with that of the pristine electrode materials, showing
Mn−LCP is not recovered and Mn(II) ions have different
chemical environments in the pristine and charge electrode
materials. To further ascertain the valence state of manganese
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after the first discharge, XPS spectra of the Mn−LCP samples
taken before and after the first discharge processes were
recorded (Supporting Information, Figure S3). As shown in
Figure S3, Supporting Information, the XPS spectrum of
pristine Mn−LCP (Supporting Information, Figure S3a) is
different from that of the Mn−LCP sample performed after the
first discharge (Figure S3b, Supporting Information), indicating
the varied chemical state of the manganese element. In Figure
S3a, Supporting Information, the two peaks appearing at 641.8
and 653.9 eV can be assigned to Mn2p3/2 and Mn2p1/2 of
Mn(II) ions, respectively,39 while in Figure S3b, Supporting
Information, the two peaks appearing at 638.5 and 650 eV can
be assigned to Mn2p3/2 and Mn2p1/2 of metallic manganese,
respectively. The binding energy difference of 11.5 eV between
Mn2p3/2 and Mn2p1/2 is in accord with the value reported in
the literature.39 These facts all confirm formation of metallic
manganese after the first discharge. In addition, because the
change of the coordination environment of the metal ion can
result in a slight change of its binding energy,39 the two peaks
appearing at 641.1 and 653.6 eV can be also assigned to
Mn2p3/2 and Mn2p1/2 of Mn(II) ions, respectively, which
indicate Mn(II) ions still exist in the sample after the first
discharge. These Mn(II) ions may be a result from the
oxidation product of metallic manganese during the sample
transfer process/the unreduced Mn(II) ions during the first
discharge process.
Though its capacity is not considerable high due to the
conversion reaction of Mn−LCP, the lower capacity problem of
metal coordination polymer materials may be solved by
applying a compound containing variable valence metal ions
(FeIII ion et al), as 3D compound FeIII(OH)0.8F0.2[O2C−
C6H4−CO2],26 which is stable during lithium-ion insertion and
extraction. Thus, it is possible to obtain stable 2D metal
coordination polymers with good electrochemical performance
via self-assembly of variable-valence metal ions and organic
ligands with low molecular weight. It might be a new route to
look for electrode materials of lithium cells from 2D metal
coordination polymers. Further investigation based on 2D
coordination polymers is still in progress.
ASSOCIATED CONTENT
* Supporting Information
TGA curve, IR spectra, XPS spectra, CIF file. This material is
■
S
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: liuqi62@163.com; Guoxiu.Wang@uts.edu.au.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
On the basis of the experimental results above, we speculate
that the possible conversion reaction in the Mn−LCP electrode
could be expressed as
This work was financially supported by the Australian Research
Council (ARC) through the ARC Discovery project
(DP077299), the National Science Foundation of China (No.
20671045, 20971060), the International Science and Technol-
ogy Cooperation Project of Changzhou City (CZ20110023),
and the Project Funded by the Priority Academic Program
Development of Jiangsu Higher Education Institutions.
[Mn(tfbdc)(4, 4′‐bpy)(H2O)2] + 2Li+ + 2e
→ Mn + [Li2(tfbdc)(4, 4′‐bpy)]
(1)
In the first discharge process, [Mn(tfbdc)(4,4′-bpy)(H2O)2]
reacts with Li via conversion reaction, leading to formation of
Mn, and the tfbdc compound of Li ions (using [Li2(tfbdc)(4,4′-
bpy)] stand for it), as shown in eq 1. A similar conversion
reaction has been observed in a 3D Zn3(HCOO)6 MOF
electrode.40 Large irreversible capacity loss (ICL) at the first
charge cycle might be attributed to the coordination water of
Mn−LCP and electrolyte decomposition, as observed in
Zn(HCOO)2·2H2O electrode,40 while ICL is mainly due to
electrolyte decomposition after the first cycle. Similar
irreversible cycle phenomena have been also observed in
SnO2 nanowires and graphene electrodes for lithium
batteries.41 For reducing ICL, prelithiation of the Mn−LCP-
based electrode42 and tailoring of the inherent transport
properties of coordination polymers may be good routes.
Besides, except for the contribution from the Mn(II)/Mn pair,
the capacity of the Mn−LCP electrode material might be also
related to the capacitive contribution and the pseudocapacitive
contribution as MnCO3 electrode material.38 Further study will
be needed to learn about more detailed electrochemical
behavior of the Mn−LCP electrode.
REFERENCES
■
(1) Fer
́
ey, G. Chem. Soc. Rev. 2008, 37, 191.
(2) Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004,
43, 2334.
(3) (a) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.;
O’Keeffe, M.; Yaghi, O. M. Science 2003, 300, 1127. (b) Choi, H. J.;
̆ ̆
Dinca, M.; Long, J. R. J. Am. Chem. Soc. 2008, 130, 7848. (c) Dinca,
M.; Long, J. R. Angew. Chem., Int. Ed. 2008, 47, 6766. (d) Jeon, Y. M.;
Armatas, G. S.; Heo, J.; Kanatzidis, M. G.; Mirkin, C. A. Adv. Mater.
2008, 20, 2105.
(4) (a) Li, H.; Eddaoudi, M.; Groy, T. L.; Yaghi, O. M. J. Am. Chem.
Soc. 1998, 120, 8571. (b) Millward, A. R.; Yaghi, O. M. J. Am. Chem.
Soc. 2005, 127, 17998. (c) Deng, H.; Doonan, C. J.; Furukawa, H.;
Ferreira, R. B.; Towne, J.; Knobler, C. B.; Wang, B.; Yaghi, O. M.
Science 2010, 327, 846. (d) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.;
Wachter, J.; O’Keeffe, M.; Yaghi, O. M. Science 2002, 295, 469.
(5) (a) Wang, B.; Cote, A. P.; Furukawa, H.; O’Keeffe, M.; Yaghi, O.
̂ ́
M. Nature 2008, 453, 207. (b) Cychosz, K. A.; Wong-Foy, A. G.;
Matzger, A. J. J. Am. Chem. Soc. 2008, 130, 6938.
(6) (a) Ohara, K.; Kawano, M.; Inokuma, Y.; Fujita, M. J. Am. Chem.
Soc. 2010, 132, 30. (b) Fujita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K.
J. Am. Chem. Soc. 1994, 116, 1151. (c) Ma, L. Q.; Abney, C.; Lin, W. B.
Chem. Soc. Rev. 2009, 38, 1248. (d) Zou, R. Q.; Sakurai, H.; Han, S.;
Zhong, R. Q.; Xu, Q. J. Am. Chem. Soc. 2007, 129, 8402. (e) Hasegawa,
S.; Horike, S.; Matsuda, R.; Furukawa, S.; Mochizuki, K.; Kinoshita, Y.;
Kitagawa, S. J. Am. Chem. Soc. 2007, 129, 2607.
4. CONCLUSION
We successfully synthesized the 2D Mn-based coordination
polymer [Mn(tfbdc)(4,4′-bpy)(H2O)2], Mn−LCP. Mn−LCP
exhibited a very weak antiferromagnetic coupling between
Mn(II) ions. When Mn−LCP was applied as an anode material
in lithium-ion cells, it delivered an irreversible high capacity in
the first discharge process and a reversible lithium storage
capacity up to about 390 mA h/g from the fourth cycle.
(7) Horcajada, P.; Serre, C.; Maurin, G.; Ramsahye, N. A.; Balas, F.;
Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Fer
2008, 130, 6774.
(8) (a) Milon, J.; Daniel, M.; Kaiba, A.; Guionneau, P.; Brandes
́
ey, G. J. Am. Chem. Soc.
́
, S.;
Sutter, J. J. Am. Chem. Soc. 2007, 129, 13872. (b) Cui, H.; Wang, Z.;
2821
dx.doi.org/10.1021/ic301579g | Inorg. Chem. 2013, 52, 2817−2822

Inorganic Chemistry
Article
Takahashi, K.; Okano, Y.; Kobayashi, H.; Kobayashi, A. J. Am. Chem.
Soc. 2006, 128, 15074.
(9) Guo, Z.; Cao, R.; Wang, X.; Li, H.; Yuan, W.; Wang, G.; Wu, H.;
(36) (a) Liu, Q.; Li, Y. Z.; Song, Y.; Liu, H. J.; Xu, Z. J. Solid State
Chem. 2004, 177, 4701. (b) Li, X. M.; Wang, C. F.; Ji, Y.; Kang, L. C.;
Zhou, X. H.; Zuo, J. L.; You, X. Z. Inorg. Chem. 2009, 48, 9166.
(37) (a) Catalina, R. P.; Pablo, A. L.; María, H. M.; Milagros, L. M.;
Pedro, G. Crystal Growth Des. 2004, 4, 57. (b) Li, M.; Xu, Z.; You, X.;
Dong, Z.; Guo, G. Polyhedron 1993, 12, 921. (c) Li, M.; Xie, G. Y.; Gu,
Y. D. Polyhedron 1995, 14, 1235.
(38) Mirhashemihaghighi, S.; Leon, B.; Vicente, C. P.; Tirado, J. L.;
́
Stoyanova, R.; Yoncheva, M.; Zhecheva, E.; Puche, R. S.; Arroyo, E.
M.; de Paz, J. R. Inorg. Chem. 2012, 51, 5554.
(39) Wagner, C. D.; Riggs, W. M.; Davis, L. E.; Moulder, J. F.;
Muilenberg, G. E. Handbook of X-Ray Photoelectron Spectroscopy;
Perkin-Elmer Corp.: Eden Prairie, MN, 1979.
(40) Saravanan, K.; Nagarathinam, M.; Balaya, P.; Vittal, J. J. J. Mater.
Chem. 2010, 20, 8329.
Li, J. J. Am. Chem. Soc. 2009, 131, 6894.
(10) (a) Bauer, C. A.; Timofeeva, T. V.; Settersten, T. B.; Patterson,
B. D.; Liu, V. H.; Simmons, B. A.; Allendorf, M. D. J. Am. Chem. Soc.
2007, 129, 7136. (b) Zhao, B.; Chen, X. Y.; Cheng, P.; Liao, D. Z.;
Yan, S. P.; Jiang, Z. H. J. Am. Chem. Soc. 2004, 126, 15394.
(11) Li, H.; Eddaoudi, M.; O’Keeffe, M.; Yaghi, O. M. Nature 1999,
402, 276.
(12) Loiseau, T.; Serre, C.; Huguenard, C.; Fink, G.; Taulelle, F.;
Henry, M.; Bataille, T.; Fer
(13) Ryo, K.; Fumiyasu, I.; Ryotaro, M.; Kitagawa, S.; Kubota, Y.;
́
ey, G. Chem.Eur. J. 2004, 10, 1373.
Takata, M.; Kobayashi, T. C. Inorg. Chem 2004, 43, 6522.
(14) Mitsuhiro, I.; Satoru, O. Inorg. Chim. Acta 2004, 357, 1039.
(41) (a) Park, M. S.; Wang, G. X.; Kang, Y. M.; Wexler, D.; Dou, S.
X.; Liu, H. K. Angew. Chem., Int. Ed. 2007, 46, 750. (b) Wang, G. X.;
Wang, B.; Wang, X.; Park, J.; Dou, S. X.; Ahn, H.; Kim, K. J. Mater.
Chem. 2009, 19, 8378.
(42) Hassoun, J.; Lee, K.-S.; Sun, Y.-K.; Scrosati, B. J. Am. Chem. Soc.
2011, 133, 3139.
(15) Rau, S.; Bottcher, L.; Schebesta, S.; Stollenz, M.; Gorls, H.;
̈
̈
Walther, D. Eur. J. Inorg. Chem. 2002, 2800.
(16) Chen, B. L.; Yang, Y.; Fatima, Z.; Qian, G. D.; Luo, Y. S.; Zhang,
J. H.; Lobkovsky, E. B. Inorg. Chem 2006, 45, 8882.
(17) Hyungphil, C.; Danil, N. D.; Hyunuk, K.; Kim, K. Chem.Eur.
J. 2005, 11, 3521.
(18) Zhu, E. J.; Liu, Q.; Chen, Q.; He, M. Y.; Chen, S. C.; Huang, H.;
Yang, Q. Chin. J. Inorg. Chem. 2008, 24, 1428.
(19) (a) Zhu, E. J.; Liu, Q.; Chen, Q.; He, M. Y.; Chen, S. C.; Huang,
H. J. Coord. Chem. 2009, 62, 2449. (b) Cheng, M. L.; Zhu, E. J.; Liu,
Q.; Chen, S. C.; Chen, Q.; He, M. Y. Inorg. Chem. Commun. 2011, 14,
300.
(20) Gopalan, R.; Muralee, M.; Carolina, S. E.; Monica, S.; Wolfgang,
W.; Madeleine, H.; Chris, M.; Jim, R.; Simon, J. T.; George, C.; Euan,
K. B. J. Am. Chem. Soc. 2004, 126, 15445.
(21) Hulvey, Z.; Falcao, E. H. L.; Eckert, J.; Cheetham, A. K. J. Mater.
Chem. 2009, 19, 4307.
(22) Feller, R. K.; Cheetham, A. K. Dalton Trans. 2008, 2034.
(23) Phuengphai, P.; Youngme, S.; Gamez, P.; Reedijk, J. Dalton
Trans. 2010, 39, 7936.
(24) (a) Armand, M.; Tarascon, J. M. Nature 2008, 451, 652.
(b) Kang, K. S.; Meng, Y. S.; Breger, J.; Grey, C. P.; Ceder, G. Science
2006, 311, 977. (c) Whittingham, M. S. Chem. Rev. 2004, 104, 4271.
(25) (a) Walker, W.; Grugeon, S.; Mentre, O.; Laruelle, S.; Tarascon,
J. M.; Wudl, F. J. Am. Chem. Soc. 2010, 132, 6517. (b) Han, X. Y.;
Chang, C. X.; Yuan, L. J.; Sun, T. L.; Sun, J. T. Adv. Mater. 2007, 19,
1616.
(26) Fer
́
ey, G.; Millange, F.; Morcrette, M.; Serre, C.; Doublet, M. L.;
Greneche, J. M.; Tarascon, J. M. Angew. Chem., Int. Ed. 2007, 46, 3259.
̀
(27) Li, X. X.; Cheng, F. Y.; Zhang, S. N.; Chen, J. J. Power Sources
2006, 160, 542.
(28) Tran-Van, P.; Barthelet, K.; Morcrette, M.; Herlem, M.;
Tarascon, J. M.; Cheetham, A. K.; Fer
Syst. 2003, 6, 29.
́
ey, G. J. New Mater. Electrochem.
(29) Cheng, C. Y.; Fu, S. J.; Yang, C. J.; Chen, W. H.; Lin, K. J.; Lee,
G. H.; Wang, Y. Angew. Chem. 2003, 115, 1981; Angew. Chem., Int. Ed.
2003, 42, 1937.
(30) (a) Goodenough, J. B.; Kim, Y. Chem. Mater. 2010, 22, 587.
(b) Kim, Y.; Arumugam, N.; Goodenough, J. B. Chem. Mater. 2008,
20, 470. (c) Combarieu, G.; Hamelet, S.; Millange, F.; Morcrette, M.;
Tarascon, J. M.; Fer
11, 1881.
́
ey, G.; Walton, R. I. Electrochem. Commun. 2009,
(31) (a) Satya Kishore, M.; Pralong, V.; Caignaert, V.; Varadaraju, U.
V.; Raveau, B. Solid State Sci. 2008, 10, 1285. (b) Daidouh, A.; Veiga,
M. L.; Pico, C. Solid State Ionics 1998, 106, 103.
(32) Sheldrick, G. M. SHELXTL-97, Program for X-ray Crystal
Structure Determination; Gottingen University: Germany, 1997.
̈
(33) (a) Zheng, X. J.; Li, L. C.; Gao, S.; Jin, L. P. Polyhedron. 2004,
23, 1257. (b) Ma, C.; Chen, C.; Liu, Q.; Liao, D.; Li, L.; Sun, L. New J.
Chem. 2003, 27, 890.
(34) Liu, Q.; Li, B. L.; Xu, Z.; Sun, X. Q.; Yu, K. B. Transition Met.
Chem 2002, 27, 786.
(35) Liu, Q.; Li, B. L.; Xu, Z.; Yu, K. B. J. Coord. Chem. 2003, 56, 771.
2822
dx.doi.org/10.1021/ic301579g | Inorg. Chem. 2013, 52, 2817−2822