Synthesis, crystal structure and photoelectric property of Mn(II/IV) coordination complexes

Article abstract of DOI:10.1016/j.ica.2008.07.010

Three novel coordination complexes [Mn(tpha)(phen)]_n (1); [Mn(na)₂(H₂O)₂]_n (2); {[Mn(phen)₂(OH)Cl] · Cl · (OH) · (C₉H₁₁NO₂) · 2H₂O} (3) have been

Full text of DOI:10.1016/j.ica.2008.07.010

Inorganica Chimica Acta 362 (2009) 1448–1454
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Synthesis, crystal structure and photoelectric property of Mn(II/IV)
coordination complexes
a
a
b
b
Li Zhang a, Shu-Yun Niu a, , Jing Jin , Li-Ping Sun , Guang-Di Yang , Ling Ye
*
a School of Chemistry and Chemical Engineering, Liaoning Normal University, Huanghe Road, Dalian 116029, PR China
b Key Laboratory of Supramolecular Structure and Materials of Ministry of Education, Jilin University, Changchun 130023, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Three novel coordination complexes [Mn(tpha)(phen)]n (1); [Mn(na)2(H2O)2]n (2); {[Mn(phen)2
(OH)Cl] ꢀ Cl ꢀ (OH) ꢀ (C9H11NO2) ꢀ 2H2O} (3) have been hydrothermally synthesized and structurally char-
acterized by single-crystal X-ray diffraction (H2tpha = terephthalic acid, Hna = nicotinic acid, phen = 1,10-
phenanthroline). The tpha groups in complex 1 bridge the Mn(II) ions to an infinite 3D framework. Com-
plex 2 exhibits a 2D network structure in which the Mn(II) ions are linked by nicotinic groups. Complex 3
is connected to a 2D coordination supramolecule by hydrogen bonds. The results of surface photovoltage
spectra (SPS) of complexes 1–3 indicate that they all exhibit positive surface photovoltage (SPV)
responses in the range of 300–800 nm. However, the intensity, position and numbers of SPV responses
are obviously different. The distinctions can be mainly attributed to their structures, valences and coor-
dination environments of the manganese ions in the three complexes. Moreover the external field
induced surface photovoltage spectra (FISPS) of the three complexes have been measured.
Ó 2008 Elsevier B.V. All rights reserved.
Received 11 March 2008
Received in revised form 3 July 2008
Accepted 9 July 2008
Available online 15 July 2008
Keywords:
Manganese (II/IV)
Coordination complex
Synthesis
Crystal structure
Surface photovoltage
1. Introduction
The surface photovoltage spectroscopy (SPS) technique, a
very sensitive characterization method which detects the
change of charge distribution on a solid material surface, is
not only related to the electron transition process caused by
light absorption but also directly reflects the property of
photogenerated charge separation and charge transfer [19–21].
At present, this technique has been successfully employed for
the study of the charge transfer in photo-stimulated surface
interactions, dye sensitization processes, photo-catalysis and
the process of charge transition between solid materials sur-
faces and phases [22–25]. Based on the SPS, Wang et al. have
developed an external field induced surface photovoltage tech-
nique [26,27], which can demonstrate the photoelectric prop-
erty of solid material surface under the effect of an external
electric field. In this paper, we report the syntheses, crystal
structures and surface photoelectric properties of three Mn(II/
IV) coordination complexes. Furthermore we compare and ana-
lyze the influences of different structures, valences and coordi-
nation environments on photoelectric properties of the
complexes.
Manganese ions play important roles in biological redox sys-
tems. They are necessary for glucose and fat oxidation processes
as well as other basic biochemistry functions [1–5]. Because the
valences of manganese ions are rich and the electronic structures
are diverse, manganese complexes with different oxidation states,
configurations and dimensions have been widely focused by
researchers [6–10]. The extensive studies of manganese coordina-
tion complexes indicate that they possess potential applications in
molecular magnet, medicine synthesis, biochemistry, catalysis and
many other domains [11–16].
The energy gaps of some transitional metal polymers are some-
times in the region of the gaps of semiconductors. This phenomenon
means that they can show certain semiconductor characteristic and
therefore be considered as some type of inorganic–organic hybrid
semiconductors. The detection about surface charge behaviors and
photoelectric properties of transitional metal coordination poly-
mers will provide special references for further research on the func-
tions of these complexes. At present, the researches about this
aspect have been mainly focused on compounds with porphyrins
and phthalocyanines as ligands, however, there are few reports on
coordination polymers [17,18].
2. Experimental
2.1. Materials and apparatus
All reagents were of A.R. grade. Infrared (IR) spectra were re-
corded on a JASCO FT-IR/480 Spectrophotometer in the range of
* Corresponding author. Fax: +86 411 82156832.
E-mail address: syniu@sohu.com (S.-Y. Niu).
0020-1693/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2008.07.010

L. Zhang et al. / Inorganica Chimica Acta 362 (2009) 1448–1454
1449
220–4000 cmꢁ1 using KBr pellets. UV–Vis spectra were obtained
Table 1
Summary of data collections and structure refinements for complexes 1, 2 and 3
on a JASCO UV/Vis/NIR UV-570 Spectrophotometer in the range
of 200–800 nm using solid powder. The elemental analysis of the
complexes was determined by a PE-240C Analyzer and a PLA-
SAM-SPEC-II instrument. SPS and FISPS measurements were con-
ducted with the light source-monochromator-lock-in detection
technique. All the measurements were performed under atmo-
spheric pressure at ambient temperature.
1
2
3
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
C20H12N2MnO4
399.26
293(2)
monoclinic
C2/c
17.436(7)
10.313(5)
9.294(6)
90
96.18(2)
90
1661.6(16)
4
C12H12N2MnO6
335.18
293(2)
monoclinic
P2(1)/c
8.7340(17)
10.182(2)
7.1369(14)
90
99.98(3)
90
625.1(2)
2
C33H33N5Cl2MnO6
721.48
293(2)
triclinic
ꢀ
P1
11.130(4)
11.517(4)
14.803(5)
70.401(5)
85.326(5)
72.829(5)
1707.5(11)
2
1.403
746
1.023
10768/7880
b (Å)
c (Å)
2.2. Synthesis of complexes 1, 2 and 3
a
(°)
b (°)
[Mn(tpha)(phen)]n (1): A solution of MnCl2 ꢀ 4H2O (0.19 g,
0.96 mmol) in water (10 mL) was added to an ethanol solution
(10 mL) of H2tpha (0.17 g, 0.97 mmol), and then phen (0.05 g,
0.97 mmol) was added into the above solution. The color of the
solution turned yellow. The mixture was then transferred into a
Teflon-lined stainless steel vessel that was sealed and heated to
170 °C for 5 days. Having been cooled to room temperature, yellow
crystals of complex 1 were collected. Yield: 0.260 g (67.9%) Anal.
Calc. for C20H12N2O4Mn: C, 60.17; H, 3.03; N, 7.02; Mn, 13.76.
Found: C, 59.85; H, 2.91; N, 7.10; Mn, 13.35%. IR data (KBr
c
(°)
V (Å3)
Z
Dcalc (g cmꢁ3
F(000)
)
1.596
812
1.077
7972/1895
1.781
342
1.086
5973/1429
Goodness-of-fit on F2
Reflections collected/
unique
Data/restraints/
parameters
1895/0/123
1429/0/97
7880/0/516
Final R indices [I > 2
r
(I)]
R1 = 0.0304,
wR2 = 0.0730
R1 = 0.0382,
wR2 = 0.0759
0.314 and
R1 = 0.0388,
wR2 = 0.1056
R1 = 0.0429,
wR2 = 0.1083
1.220 and
R1 = 0.0608,
wR2 = 0.1304
R1 = 0.1177,
wR2 = 0.1595
0.457 and
pellet, cmꢁ1): 3441 (
m
–OH); 3062 (
m
Ar–H); 1597 (mas–cooꢁ); 1385
R indices (all data)
. . .
(ms–cooꢁ); 1513, 1495, 1425 (mC C); 845, 806 (Ar–H); 750 (
m
Mn–O);
•
Largest difference peak
and hole (e Åꢁ3
505 (mMn–N).
)
ꢁ0.276
ꢁ0.735
ꢁ0.431
[Mn(na)2(H2O)2]n (2):
A
solution of MnCl2 ꢀ 4H2O (0.19 g,
0.96 mmol) in water (10 mL) was added to a solution of nicotinic
acid (0.12 g, 1.0 mmol) and NaOH (0.04 g, 1.00 mmol) in water
(10 mL). The solution was colorless. Then the mixture was trans-
ferred into a Teflon-lined stainless steel vessel, and the vessel
was sealed and heated to 170 °C for 5 days. Having been cooled
to room temperature, colorless crystals of complex 2 were col-
lected. Yield: 0.126 g (39.2%). Anal. Calc. for C12H12N2O6Mn: C,
43.00; H, 3.61; N, 8.36; Mn, 16.39. Found: C, 42.20; H, 3.48; N,
3. Results and discussion
3.1. Structural description of complexes 1, 2 and 3
The single-crystal X-ray diffraction analysis revealed that com-
plex 1 exhibits a 3D infinite framework structure. The unit coordi-
nation is defined by four O atoms from four different tpha groups
and two N atoms from one phen ligand around the Mn(II) ion in
a distorted octahedronal fashion (Fig. 1). The bond length of Mn–
N is 2.3440(18) Å and the distances of Mn–O are 2.1145(14) Å
and 2.1369(15) Å, respectively. All the tpha groups can be sepa-
rated into two categories (A and B) according to their space posi-
tions. The phenyl rings of the A kind (or B kind) are coplanar,
while the phenyl rings between the A kind and B kind are twisted
by 67.2°.
In crystal, tpha groups of A kind use four carboxylic O atoms to
coordinate four different Mn(II) ions, which in turn are joined to a
1D chain along the a-axis direction. Along c-axis, tpha groups of B
kind coordinate two adjacent Mn(II) ions through two carboxylic O
atoms by a bidentate bridging mode which makes the Mn(II) ions
connect to a 2D structure in ac layer (Fig. 2). Between the two 2D
layers, the other carboxylic O atoms of B kind tpha groups adopt
the same mode to link adjacent Mn(II) ions (Fig. 3). Therefore,
Mn(II) ions are further connected to a 3D infinite structure (Sup-
plementary Fig. 1s). When projected along c-axis, it can be seen
clearly that the layers cross each other and form many regular loz-
enge holes. All the phen molecules arrange regularly in the lozenge
holes (Fig. 4). The regular structure is beneficial for transferring
electrons or holes.
8.54; Mn, 16.11%. IR data (KBr pellet, cmꢁ1): 3306 (
m
–OH); 3043
. . .
(
m
Ar–H); 1612 (mas–cooꢁ); 1393(ms–cooꢁ); 1594, 1563, 1427 (mC C);
•
1197 (–OH); 1160, 1045 (mC–N
Mn–O); 419( Mn–N).
[Mn(phen)2(OH)Cl] ꢀ Cl ꢀ OH ꢀ 2H2O ꢀ C9H11NO2 (3): A solution of
, C–O); 862, 755, 701 (Ar–H); 555
(m
m
MnCl2 ꢀ 4H2O (0.19 g, 0.96 mmol) in water (10 mL) was added to a
solution of 4-aminobenzoic acid (0.15 g, 1.09 mmol) and NaOH
(0.04 g, 1.00 mmol) in water (10 mL), and then phen (0.05 g,
0.97 mmol) and ethanol solution (5 mL) was added into the above
solution. The color of the solution turned red. The mixture was
transferred into a Teflon-lined stainless steel vessel that was sealed
and heated to 170 °C for 5 days. Having been cooled to room tem-
perature, red crystals of complex 3 were collected. Yield: 0.296 g
(42.8%). Anal. Calc. for C33H33N5Cl2O6Mn: C, 54.94; H, 4.61; N,
9.71; Mn, 7.61. Found: C, 54.37; H, 4.35; N, 9.89; Mn, 7.39%. IR data
(KBr pellet, cmꢁ1): 3563 (
m–NH); 3050 (mAr–H); 2994, 2929, 2609
(
m–OH
,
m
–NH); 1620 (mas–cooꢁ); 1424 (ms–cooꢁ); 1589, 1572, 1514,
. . .
1492 (mC C); 1221 (–OH); 1141, 1100, (mC–N, mC–O); 860, 728
•
(Ar–H); 637 (mMn–O); 418 (mMn–N); 276 (mMn–Cl).
2.3. Determination of crystal structure
Crystallographic data for complexes 1 and 2 were collected on a
Rigaku R-AXIS-RAPID diffractometer using graphite monochromat-
Complex 2 possesses a 2D infinite structure and its building unit
is [Mn(na)2(H2O)2]. Each Mn(II) ion is six coordinated. Two N atoms
and two O atoms are from four different nicotinic groups, and two O
atoms are from two coordinated water molecules. The coordination
environment of Mn(II) ion is a slightly distorted octahedron (Fig. 5).
The bond lengths of Mn–O range from 2.1632(17) Å to 2.1835(17) Å
and Mn–N are 2.2860(19) Å. O1 and O1C, O3 and O3C, N1A and N1D
are all centro-symmetric for Mn(II) ion. One N atom and one car-
boxylic O atom from the nicotinic group coordinate two different
ed Mo K
for complex 3 was collected on a Smart APEX II CCD diffractometer
using graphite monochromated Mo K radiation (k = 0.71073 Å) at
a radiation (k = 0.71073 Å) at 293 K. Crystallographic data
a
293 K. All data were corrected for Lorentz polarization factor and
empirical absorption. The structures were solved by direct method
and refined by full matrix least-squares calculations on F2 using
SHELXTL 97 program. The crystal data and structure refinement of
complexes 1–3 are summarized in Table 1.

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L. Zhang et al. / Inorganica Chimica Acta 362 (2009) 1448–1454
Fig. 3. bc layer of complex 1 (Phen molecules are omitted for clarity).
Mn(II) ions, and then the Mn(II) ions are connected to a 1D zigzag
chain along b-axis (Supplementary Fig. 2s). Nicotinic groups link
Mn(II) ions in adjacent chains by the same mode as described
above, which makes the Mn(II) ions link another 1D chain along
c-axis. Therefore, complex 2 is further connected to a 2D infinite
structure in bc plane (Fig. 6).
Complex 3 is an ionic complex. The molecular structure is given
in Fig. 7. In cation, the six coordination atoms of Mn(IV) are from
two phen molecules, one hydroxyl and a chlorine anion. One
chlorine anion, one hydroxyl, two free water molecules and one
4-aminobenzoate consist of the outside environment. Since none
of 4-aminobenzoate was added to the starting reaction mixture,
we speculate that it may be the result of reaction between 4-
aminobenzoic acid and ethanol.
In crystal, water molecules, hydroxyl, chlorine anions and N
atoms of 4-aminobenzoate join together to form the construction
of the hydrogen bond web. Two coordinated hydroxyl and two free
water as well as two free chlorine anions form a six-membered
ring (Supplementary Fig. 3s). O6 atom from free water molecule
connects O5 atom in the six-membered ring and Cl2 anion, which
links Mn(IV) ions to a 1D chain along b-axis (Fig. 8). N atoms of two
4-aminobenzoate join Cl1 anion to another 1D chain along a-axis,
therefore complex 3 is connected to 2D net-like structure in ab
plane (Supplementary Fig. 4s). Hydrogen bond data for complex
3 are given in Supplementary Table 1s and selected bond lengths
and bond angles are also listed in Supplementary Table 2s.
Fig. 1. Coordination environment of Mn(II) ion in complex 1.
3.2. SPS of complexes 1, 2 and 3
The surface photovoltage spectra were measured with a home-
built apparatus described in Supplementary Figs. 5s and 6s in the
range of 300–800 nm. A signal detected by SPS is equivalent to
the change in the surface potential barrier on illumination (dVs),
which is given by the equation dVs ¼ Vs ꢁ V0, where V0 and Vs
s
s
are the surface potential barriers before and after illumination,
respectively [28]. The principles of SPS (Figs. 7s and 8s) and the
analysis for spectral bands (Fig. 9s) are described in Supplemen-
tary material. The electrode is made of optical glass coated with in-
dium and tin oxides (ITO). Standard p-typed silicon flake is used to
adjust comparative phase and xenon lamp is used as an illuminant
to supply a radiation in the range of 300–800 nm. The crystals are
powdered and put into sample cell which is consisted of an ITO/
sample/ITO sandwich structure. In order to make the light radiate
the sample perpendicularly, the position of sample cell is adjusted
and the surface photovoltage and external field induced surface
Fig. 2. ac layer of complex 1 (Phen molecules are omitted for clarity).

L. Zhang et al. / Inorganica Chimica Acta 362 (2009) 1448–1454
1451
Fig. 4. The projection along c-axis of complex 1.
in the range of 300–550 nm. The SPV response at kmax = 343 nm
is attributed to the
p* transition of ligands and the response
p
?
at kmax = 375 nm is assigned to the LMCT transition while the re-
sponse at kmax = 429 nm can be assigned to the d ? d* transition
(2T2 ? 2A2, 2T2) of Mn(II) ion. Because the Mn(II) ion in complex
2 lies in a stronger crystal-field and the transitions of 2T2 ? 2A2,
2T2 are allowed, the response at kmax = 429 nm can be clearly
observed.
In the SPS of complex 3 (Fig. 11), three positive response bands
in 300–650 nm were observed. The SPV response with the higher
energy can be divided into two bands: kmax = 334 nm and
kmax = 364 nm. They can be attributed to
p ?
p* transition of li-
gands and LMCT, respectively. The two lower responses at
kmax = 440 nm and kmax = 557 nm can be assigned to the d ? d*
transitions of Mn(IV) ion (4A2 ? 4T1 and 4A2 ? 4T2) in a stronger
crystal-field. The SPS spectra of the three complexes are consistent
with their UV–Vis spectra. The UV–Vis spectra of the three com-
plexes are treated by ORIGIN 7.0 and displayed in Supplementary
Figs. 10s, 11s and 12s. The analysis and contrast of SPS and UV–
Vis spectroscopy of the three complexes are listed in Supplemen-
tary Table 3s.
Two differences are shown when we compared the SPS of com-
plexes 1–3 (Fig. 12). First of all, the SPV intensity of complexes de-
creases gradually from 1–3, mainly because of the different
structure of the three complexes: Complex 1 possesses a 3D infi-
nite structure which can supply more transmission passages for
electrons or holes. More electrons diffuse to surface can lead an in-
crease of SPV intensity. Meanwhile, the ac plane and bc plane in
complex 1 are both regular, which is very favorable for transmit-
ting electrons or holes. Complex 2 possesses an irregular 2D struc-
ture, which is less favorable for transferring electrons or holes than
the regular one. So the SPV intensity of complex 1 is higher than
that of complex 2. Complex 3 is a mononuclear complex and the
molecules are further connected to 2D structure by hydrogen
bonds. So the SPV intensity of complex 3 is obviously lower than
that of complexes 1 and 2. Secondly, the position of d ? d* transi-
tion is obviously different, which can be attributed to the coordina-
tion environment and valences of manganese ions in the three
complexes. As same as complex 1, the six coordinated atoms of
Fig. 5. Coordination environment of Mn(II) ion in complex 2.
photovoltage under
measured.
a discontinuous electric field have been
Fig. 9 shows the SPS of complex 1 in which there is a wide and
strong response band within 300–475 nm. After treated by pro-
gram ORIGIN 7.0 [17], the response band can be divided into two po-
sitive responses. The response at kmax = 351 nm is attributed to the
p
? p
* transition of ligands while the response at kmax = 383 nm is
assigned to the LMCT transition (from ligand to metal charge trans-
fer transition). Meanwhile, there are some weak and splitting
peaks in 475–550 nm, which are caused by d ? d* transition
(6A1 ? 4T1) of Mn(II, d5) ion in a weaker crystal-field coordination
environment.
The SPS of complex 2 (Fig. 10) shows a broad response band
which seemed to be an overlap of three positive response bands

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L. Zhang et al. / Inorganica Chimica Acta 362 (2009) 1448–1454
Fig. 6. The 2D infinite structure of complex 2.
Mn(II) ion are two N atoms and four O atoms in complex 2. The dif-
ference between complexes 1 and 2 is that the four O atoms are all
from carboxylic moieties in complex 1, while only two O atoms are
from carboxylic moieties and the other O atoms are from coordi-
nated water molecules in complex 2. According to the spectra
chemical series (–COO < H2O < N complexes), Mn(II, d5) ion in com-
plex 1 can be regarded as lying among a weaker crystal-field, so the
d?d* transition is forbidden. In complex 2, Mn(II) ion is in a stron-
ger octahedron field and the transitions of 2T2 ? 2A2 and 2T2 ? 2T2
are allowed, so the SPV response of d ? d* transition can be ob-
served. In complex 3, the valence of manganese ion is +4 and the
coordinated atoms are four N atoms, one O atom and one Cl anion.
The Mn(IV, d3) ion is lying in a stronger field and the transitions of
4A2 ? 4T1 and 4A2 ? 4T2 are allowed, so it shows two obvious re-
sponse bands of d ? d* transitions in the SPS.
3.3. FISPS of complexes 1, 2 and 3
FISPS is a technique which combines the field effect principle
with SPS. With a discontinuous d.c. electric field applying to both
sides of the sample, the mobile direction and diffusive distance
of photogenerated charge will vary, even the built-in field of the
sample could change direction. If a positive electric field (the illu-
minated surface is positive) is applied vertically to the p-typed
semiconductor surface, the separation efficiency of the photogen-
eration charge will enhance and the intensity of SPV response will
Fig. 7. Molecular structure of complex 3.

L. Zhang et al. / Inorganica Chimica Acta 362 (2009) 1448–1454
1453
Fig. 10. SPS of complex 2 (dotted lines are peaks treated by ORIGIN 7.0).
Fig. 8. Hydrogen bonds in b-axis of complex 3.
Fig. 11. SPS of complex 3 (dotted lines are peaks treated by ORIGIN 7.0).
Fig. 9. SPS of complex 1 (dotted lines are peaks treated by ORIGIN 7.0).
increase in the original direction. However, if a negative electric
field in the opposite direction is applied to the built-in field, the
separation efficiency of electrons and holes will reduce so that
the intensity of SPV responses will weaken. With the aid of FISPS,
the photo-induced charge transfer process can be detected and
even some spectral characteristics can be interpreted. Fig. 13 is
the FISPS of complex 2 when the external electric fields are
ꢁ0.5 V, ꢁ1.0 V, +0.5 V and +1.0 V, respectively. The FISPS of com-
plexes 1 and 3 (Supplementary Figs. 13s and 14s) are similar to
that of complex 2. The FISPS results indicate that the SPV response
intensity increases linearly of all three complexes when the exter-
Fig. 12. The SPS contrast of the three complexes.
nal positive fields increases; while reduces when the external neg-
ative fields increases. This is due to an external positive electric
field is in favor of the separation of photo-excited electron–hole
pairs, which in turn results in an increase of response intensity. A
negative electric field has just the opposite effect.

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L. Zhang et al. / Inorganica Chimica Acta 362 (2009) 1448–1454
Appendix A. Supplementary material
CCDC 638237, 638236 and 651307 contain the supplementary
crystallographic data for 1, 2 and 3. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.ica.2008.07.010.
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4. Conclusion
In this study, the synthesis, analysis of crystal structures, full
characterization and photoelectric property of three novel manga-
nese complexes are presented. Complexes 1 and 2 are both coordi-
nation polymers possessing 3D and 2D infinite structures
respectively. Complex 3 is a 2D coordination supramolecule con-
nected by hydrogen bonds. The surface photovoltage spectra all
show positive responses in the range 300–800 nm. But the inten-
sity, position and numbers of the SPV response bands are appar-
ently different from one another. The main reasons believed to
be the differences in structure, valence and coordination sphere
of manganese ions in the three complexes. First, the intensity of
SPV bands is affected by the structures of the complexes. More
dimensional structure can supply more transmission passages for
electrons or holes which make the SPV intensity increase. Second,
the valence of metal ion impacts the number of SPV bands. Third,
the number and position of the SPV bands can be impacted
by the coordinated environment of metal ions. When the metal
ions are in different crystal fields or even the coordinated atoms
are the only differences, it may trigger different transitions be-
tween the d orbitals of the metal ions, so the SPV response bands
will exhibit noticeable differences.
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This work was supported by the National Natural Science Foun-
dation of China (Nos. 20571037 and 90201018) and the open fund
of the State Key Laboratory of Rare Earth Material Chemistry and
Application, Peking University of China.