Syntheses, crystal structures and properties of five divalent transition metal coordination compounds based on a semirigid tetracarboxylic acid ligand

Article abstract of DOI:10.1016/j.ica.2013.08.022

Five divalent transition metal coordination compounds based on a semirigid tetracarboxylic acid have been synthesized by the hydrothermal method, namely, [MnL_0.5phen]_n (1), [CdL_0.5phen]_n (2), [Co(H₂L)(phen)₂H₂O]_n (3), {[Ni₂L(phen)₂(H₂O)₆]·2H ₂O}_n (4) {[Zn₂L(phen)₄(H ₂O)₂]·2H₂O}_n (5) (H ₄L = 1,4-bis(4-oxy-1,2-benzene dicarboxylic acid)benzene, phen = 1,10-phenanthroline). These compounds were structurally characterized by infrared spectra, thermogravimetric analyses and single crystal X-ray diffractions. The isostructural 1 and 2 exhibit the two-dimensional layered structures. Compound 3 and 4-5 reveal a mononuclear and two dinuclear structures, respectively. In addition, the magnetic property of 1 and the photoluminescence of 2 and 5 were also investigated, respectively.

Full text of DOI:10.1016/j.ica.2013.08.022

Inorganica Chimica Acta 408 (2013) 84–90
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Syntheses, crystal structures and properties of five divalent transition
metal coordination compounds based on a semirigid tetracarboxylic acid
ligand
⇑
⇑
Meihui Yu, Ming Hu , Zhenting Wu, Haiquan Su
Inner Mongolia Key Laboratory of Chemistry and Physics of Rare Earth Materials, School of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 26 April 2013
Received in revised form 27 July 2013
Accepted 27 August 2013
Available online 5 September 2013
Five divalent transition metal coordination compounds based on a semirigid tetracarboxylic acid have
been synthesized by the hydrothermal method, namely, [MnL0.5phen]n (1), [CdL0.5phen]n (2),
[Co(H2L)(phen)2H2O]n (3), {[Ni2L(phen)2(H2O)6]ꢀ2H2O}n (4) {[Zn2L(phen)4(H2O)2]ꢀ2H2O}n (5) (H4L =
1,4-bis(4-oxy-1,2-benzene dicarboxylic acid)benzene, phen = 1,10-phenanthroline). These compounds
were structurally characterized by infrared spectra, thermogravimetric analyses and single crystal
X-ray diffractions. The isostructural 1 and 2 exhibit the two-dimensional layered structures. Compound
3 and 4–5 reveal a mononuclear and two dinuclear structures, respectively. In addition, the magnetic
property of 1 and the photoluminescence of 2 and 5 were also investigated, respectively.
Ó 2013 Elsevier B.V. All rights reserved.
Keywords:
Coordination compounds
Semirigid ligand
Crystal structure
Photoluminescence
Magnetic property
1. Introduction
also been proved to be efficient building blocks in the construction
of various dimensional coordination polymers [15,16]. In addition,
Numbers of the researches in supramolecular chemistry and
crystal engineering have focused on the rational design and syn-
thesis of multifunctional metal–organic frameworks (MOFs) in
the past decade [1]. MOFs have been attracted much attentions
for their fascinating architectures and potential applications in
the fields of gas adsorption and storage, ion exchange, catalysis,
molecular magnetism and photoluminescence [2,3]. A consider-
able amount of coordination polymers with interesting structures
and well-established topologies have been successfully synthe-
sized, such as metal-carboxylates MOFs based on d-block transi-
tion and lanthanide metal ions [4,5]. In the process of building
coordination polymers, some factors must be considered for the
design of constructions, such as the length and flexibility of li-
gands, the coordination modes of the metal ions and the pH of
reaction system [6–12]. The researches about the rigid and semi-
rigid multicarboxylate ligands are still good candidates for building
MOFs, which can be attributed to the rich varieties of coordination
modes of multicarboxylate groups [13,14].
an effective and controllable route is to introduce auxiliary rigid
multidentate N-donor ligands. However, less studies about both
semirigid carboxylate ligands and auxiliary multidentate N-donor
ligands have been reported [17–21].
Herein, we select a semirigid ligand attached four carboxylate
groups in symmetrical positions, namely, 1,4-bis(4-oxy-1,2-ben-
zene dicarboxylic acid)benzene (H4L). H4L is a long tetracarboxyl-
ate ligand with two semirigid –O– spatial linkers, which can
impart a variety of connection modes with metal centers and gen-
erate abundant structural motifs [22]. Meanwhile, H4L can bond
and rotate along two semirigid –O– spacer so that it improves
the coordination ability and the structural peculiarity when it coor-
dinates to metal centers. In this paper, we have prepared five tran-
sition metal coordination compounds using the semirigid H4L by
the hydrothermal method, the structures, thermal stabilities, lumi-
nescent and magnetic properties of some complexes were explored
in detail.
In contrast to the rigid ligands with difficult conformational
changes in the assembly of coordination polymers, the semirigid li-
gands can easily regulate its configurations to enhance the struc-
tural diversity. On the other hand, the semirigid ligands have
2. Experimental
2.1. Materials and general methods
The 1,4-bis(4-oxy-1,2-benzene dicarboxylic acid)benzene was
synthesized according to the literature procedure [23]. All other re-
agents were used as received from commercial sources without
⇑
Corresponding authors. Tel.: +86 0471 4992981.
E-mail address: hm988@126.com (M. Hu).
0020-1693/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ica.2013.08.022

M. Yu et al. / Inorganica Chimica Acta 408 (2013) 84–90
85
further purification. Elemental analyses (C, H and N) were deter-
mined on Perkin-Elmer 2400 analyzer. The IR spectra were re-
corded as KBr pellets on a Nicolet Avatar-360 spectrometer in
the 400–4000 cmꢁ1 region. Thermogravimetric analysis (TGA)
was performed on a Perkin-Elmer TG-7 analyzer heated from 25
to 800 °C under air atmosphere. Powder X-ray power diffraction
(PXRD) was performed on a X’Pert PRO (PW3071/xx Bracket) dif-
1607.24(s), 1544.58(s), 1412.03(s), 1255.45(m), 1227.72(s),
1192.32(m), 814.46(m). Anal. Calc. for 3: C, 63.23; H, 3.47; N, 6.4.
Found: C, 63.25; H, 3.45; N, 6.37%.
2.2.4. Synthesis of complex {[Ni2L(phen)2(H2O)6]ꢀ2H2O}n (4)
The method of synthesis was similar to that used for 2 with the
exception that NiSO4ꢀ6H2O (0.2 mmol, 52.6 mg) was instead of
Cd(NO3)2ꢀ4H2O. The faint blue crystal of 4 was collected, washed
with H2O and air-dried. Yield 52%. IR (KBr pellet): 3439.08(s),
1630.57(s), 1493.17(m), 1424.38(s), 1259.93(m), 1218.97(s),
1184.60(m), 847.82(s), 726.25(s). Anal. Calc. for 4: C, 52.31; H,
4.02; N, 5.31. Found: C, 52.28; H, 4.00; N, 5.29%.
fractometer with Cu K
a radiation (k = 1.5406 Å). The fluorescent
spectra were measured on a FLS920 spectrophotometer.
2.2. Synthesis of complexes 1–5
2.2.1. Synthesis of complex [MnL0.5phen]n (1)
A mixture of MnCl2ꢀ4H2O (0.2 mmol, 39.6 mg), H4L (0.1 mmol,
43.8 mg), phen (0.2 mmol, 39.6 mg) and H2O (12 mL) was stirred
for 30 min at room temperature and was sealed in a 23 mL Tef-
lon-lined stainless steel vessel, heated at 160 °C for 72 h, kept
20 h at 100 °C and followed by slow cooling to the room tempera-
ture at a rate of 5 °C hꢁ1. The faint yellow crystalline product was
obtained, isolated by filtration, then washed with H2O and air-
dried, yield 61%. IR (KBr pellet): 3416.89(s), 1626.07(s),
1492.52(m),1395.14(s), 1259.36(m), 1216.01(s), 1188.37(w),
842.73(m), 725.53(m). Anal. Calc. for 1: C, 61.08; H, 2.90; N, 6.20.
Found: C, 61.04; H, 2.87; N, 6.23%.
2.2.5. Synthesis of complex {[Zn2L(phen)4(H2O)2]ꢀ2H2O}n (5)
A mixture of Zn(NO3)ꢀ6H2O (0.2 mmol, 59.5 mg), H4L (0.1 mmol,
43.8 mg), phen(0.2 mmol, 39.6 mg) in 15 mL of mixed H2O-
C2H5OH-NaOH (0.1 mmol/mL) (9:2:4,v/v/v) was placed in
a
23 mL Teflon-lined stainless steel vessel, heated at 160 °C for
72 h, kept 20 h at 100 °C, and then followed by slow cooling to
the room temperature at a rate of 5 °C hꢁ1. The colorless crystal
of 5 was collected, washed with H2O, and air-dried. Yield 50%. IR
(KBr pellet): 1682.37(s), 1588.06(m), 1500.83(w), 1433.47(m),
1301.15(s), 1188.39(m), 943.92(m), 721.81(s). Anal. Calc. for 5: C,
61.86; H, 3.68; N, 8.25. Found: C, 61.85; H, 3.66; N, 8.24%.
2.2.2. Synthesis of complex [CdL0.5phen]n (2)
Complex 2 was synthesized in a similar procedure to that de-
scribed for 1 with the exception that Cd(NO3)2ꢀ4H2O (0.2 mmol,
61.7 mg) was replaced by MnCl2ꢀ4H2O and 15 mL H2O. The color-
less crystal of 2 was collected, washed with H2O, and air-dried.
Yield 55%. IR (KBr pellet): 3432.33(s), 1665.94(w), 1571.58(m),
1492.27(s), 1374.57(s), 1272.75(m), 1216.98(s), 1183.00(m),
844.43(m), 769.60(m). Anal. Calc. for 2: C, 54.19; H, 2.58; N, 5.50.
Found: C, 54.01; H, 2.61; N, 5.48%.
2.3. X-ray crystallography
Crystallographic data for compounds 1–5 were collected on a
Bruker Apex Smart CCD diffractometer with graphite-monochro-
mated Mo Ka radiation (k = 0.71073 Å) using the x-scan technique
at room temperature. All the structures were solved by direct
methods with SHELXS-97 and refined with the full-matrix least-
squares |F| [2] technique using the SHELXL-97 [24] program. The po-
sition of non-hydrogen atoms were refined with anisotropic dis-
placement parameters. The hydrogen atoms were set in
calculated positions and refined as riding atoms with a common
isotropic thermal parameter. The crystallographic data for 1–5
are listed in Table 1. The selected bond lengths and angles of 1–5
are listed in Tables S1–S5.
2.2.3. Synthesis of complex [Co(H2L)(phen)2H2O]n (3)
The method of synthesis was similar to that used for 2 with the
exception that Co(NO3)2ꢀ6H2O (0.2 mmol, 58.2 mg) was instead of
Cd(NO3)2ꢀ4H2O. The orange crystal of 3 was collected, washed with
H2O and air-dried. Yield 57%. IR (KBr pellet): 3419.65(s),
Table 1
The crystallographic data for complexes 1–5.
Compound
1
2
3
4
5
Formula
Formula weight
T (K)
Crystal system
Space group
a (Å)
C
23H13MnN2O5
C23H13CdN2O5
509.75
293(2)
monoclinic
P21/c
7.1818(9)
18.432(3)
14.9225(18)
90.00
96.818(12)
90.00
C46H30CoN4O11
873.67
293(2)
monoclinic
P21/c
13.4288(9)
15.5207(11)
20.4934(17)
90.00
114.856(6)
90.00
3875.7(5)
4
1.497
0.515
C46H42Ni2N4O18
1056.22
293(2)
C70H50Zn2N8O14
1357.96
293(2)
452.29
293(2)
monoclinic
P21/c
7.0841(3)
18.3818(7)
14.8668(6)
90.00
96.280(4)
90.00
1924.32(13)
4
triclinic
triclinic
ꢀ
ꢀ
P1
P1
7.3598(9)
12.5630(9)
13.3038(15)
70.312(8)
78.188(10)
87.863(7)
1133.0(2)
1
10.1243(6)
11.8713(8)
13.1068(11)
83.565(6)
68.614(7)
79.565(5)
1440.74(19)
1
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
1961.4(5)
4
1.726
Z
Dcal(g cmꢁ3)
1.561
0.726
1.548
0.914
1.565
0.914
l
(mmꢁ1
)
1.153
F(000)
920
1012
1796
546
698
Rint
0.0478
1.043
0.0399
0.0726
0.0626
0.0812
0.1201
1.011
0.0552
0.1262
0.1089
0.1821
0.0658
1.016
0.0476
0.0896
0.0836
0.1053
0.0425
1.049
0.0511
0.1126
0.0741
0.1287
0.0306
1.054
0.0346
0.0785
0.0413
0.0833
Goodness-of-fit (GOF)
a
R1
b
xR2 [I > 2
r(I)]
R1 (all data)
wR2 (all data)
P
P
a
R1
=
||Fo| ꢁ |Fc||/ |Fo|.
P
P
b
2
xR2 = [
[x
(Fo ꢁ Fc2)2]/
x
(Fo2)2]1/2
.

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M. Yu et al. / Inorganica Chimica Acta 408 (2013) 84–90
by two carboxylate groups to obtain a binuclear building block.
3. Results and discussion
The building blocks are connected each other through carboxylate
groups along a axis to lead to a one-dimensional (1D) infinite zig-
zag chain (Fig. 1b). The adjacent 1D chains are further linked by the
carboxylate oxygen atoms to generate a 2D layer viewed along the
b axis (Fig. 1c). The distances between two adjacent Mn2+ ions in a
zigzag chain which are linked by the carboxylate groups are 4.2988
and 4.8516 Å, respectively, and the distance of Mn2+ ions between
two adjacent chains which are linked by the carboxylate groups is
3.1. Structural description of [MnL0.5phen]n (1)
Complex 1 crystallizes in the monoclinic system with space
group P21/c. There are one Mn(II) ion, a half of L4ꢁ and one phen
molecule in the asymmetric unit of 1. The coordination environ-
ment and atom connectivity for 1 are shown in Fig. 1a. Mn(II)
ion is six-coordinated with a distorted octahedron geometry,
which is coordinated by four O atoms (O1, O3, O2#2, and O4#1)
of monodentate carboxylate groups from three ligands and two
nitrogen atoms (N1, N2) from phen. All carboxylate groups of each
9.8312 Å. At the same time, there are weak
p–p interactions be-
tween pyridyl rings of phen and those of the phenyl rings, the dis-
tance of centroids is 3.9709 Å [26]. The Mn(II) ions and the L4ꢁ
ligands can be considered as 3-connected and 6-connected nodes,
respectively, in which Mn(II) ions are represented with the point
(Schlafli) symbol {43} and the ligands with the point (Schlafli) sym-
bol {46.66.83}. The structure can be simplified as 3,6-connected
framework with the point (Schlafli) symbol {43}2{46.66.83}
(Fig. 1d).
H4L ligand link neighboring Mn(II) ions in the the mode of l2
-
g1
:
g1 (Scheme 1a). The Mn–O bond distances range from
2.1411(19) to 2.2402(19) Å; the Mn–N bond lengths of 2.297(2)
and 2.309(2) Å are slightly longer than that of Mn–O, which are
well-matched to those observed in the reported complexes [25].
Every two crystallographically equivalent Mn(II) ions are bridged
Fig. 1. (a) Coordinated environment of Mn(II) ion (symmetry codes: #1 ꢁx + 2, ꢁy, ꢁz; #2 ꢁx + 1, ꢁy, ꢁz); (b) A view showing a 1D chain running along the a axis; (c) A view
of the 2D sheet by L4ꢁ ligand and Mn(II) along the b axis; (d) The topology of 1 (red and blue balls represent 6-connected L4ꢁ ligands and 3-connected Mn(II), respectively).

M. Yu et al. / Inorganica Chimica Acta 408 (2013) 84–90
87
Scheme 1. Coordination modes of H4L (1,4-bis(4-oxy-1,2-benzene dicarboxylic acid)benzene).
3.2. Structural description of [CdL0.5phen]n (2)
3.3. Structural description of [Co(H2L)(phen)2H2O]n (3)
Compound 2 is isostructural to 1. As shown in Fig. S1a and c, the
coordinated environment and the topology of 2 are identical to
those of 1. The Cd–O and Cd–N bond lengths range from 2.235(5)
to 2.399(6) Å and 2.375(7) to 2.395(7) Å, respectively, which are
similar to those observed in the reported complexes.[27b].
Compound 3 crystallizes in the monoclinic system with P21/c
space group. In the asymmetric unit of [Co(H2L)(phen)2H2O], there
are one Co(II) ion, one partly deprotonated H2L2ꢁ ligand, two aux-
iliary ligands phen and one coordinated water molecule. The six-
coordinated Co(II) ion is surrounded by a monodentate carboxylate
group from the H2L ligand, four nitrogen atoms from two phen, and
one oxygen atom from the water molecule (Fig. 2a). The Co–O bond
distances are 2.046(2) and 2.095(2) Å, respectively, and the Co–N
bond lengths ranges from 2.133(2) to 2.172(3) Å, which are similar
to the reported Co–O and Co–N bond distances [27]. The bond an-
gles around the Co(II) center are in the range of 77.57(9)°–
168.12(10)°. The carboxylate groups of ligands show monodentate
mode to link one Co(II) ion (Scheme 1b) to form a mononuclear
unit. The different units are connected by two kinds of intermolec-
ular hydrogen bonds. The detailed modes of hydrogen bonding are
shown in Fig. 2b, (Supporting information, Table S6). Then, the
mononuclear units are combined through the intermolecular
hydrogen bonds to form a 3D supramolecular structure (Fig. 2c).
3.4. Structural description of {[Ni2L(phen)2(H2O)6]ꢀ2H2O}n (4)
ꢀ
Complex 4 crystallizes in the triclinic system with P1 space
group. In the dinuclear structure of 4, the symmetric unit is com-
posed of two Ni(II) ions, one totally deprotonated L4ꢁ ligand, two
phen, six coordinated and two lattice water molecules. Each Ni(II)
ion is six-coordinated with a slight distorted octahedron environ-
ment by a carboxylate oxygen atom from ligand, two nitrogen
atoms from phen, and three terminal water molecules (Fig. 3a).
The carboxylate groups of ligands show monodentate mode to link
two Ni(II) ions (Scheme 1c). The Ni–O and Ni–N bond lengths range
from 2.006(3) to 2.138(3) Å, 2.069(3) to 2.071(3) Å, respectively;
the distance between two Ni(II) ions is 19.665 Å. The bond angles
around Ni(II) center range in 80.43(12)°–178.70(12)°. There are
existing hydrogen-bonding including intramolecular and intermo-
lecular interactions, which are formed between water molecules
and carboxylate oxygen atoms (Supporting information,
Table S7,). In the formation of hydrogen bondings, the uncoordi-
nated carboxylate oxygen atoms act fully as proton acceptors. Fi-
nally, the dinuclear units are extended to a 3D supramolecular
architecture by intermolecular hydrogen-bonding interactions
(Fig. 3b).
3.5. Structural description of {[Zn2L(phen)4(H2O)2]ꢀ2H2O}n (5)
ꢀ
Compound 5 has a triclinic space group P1 and also exhibits a
dinuclear structure, and the symmetric unit of 5 contains two
Fig. 2. (a) Coordinated environment of Co(II) ion. (b) The modes of hydrogen bonds.
(c) The 3D supramolecular architecture of compound 3.
Zn(II) ions, one L4ꢁ anion ligand, four phen, two coordinated and

88
M. Yu et al. / Inorganica Chimica Acta 408 (2013) 84–90
Fig. 3. (a) Coordinated environment of Ni(II) ion. (b) The 3D supramolecular architecture of 4.
Fig. 4. (a) Coordinated environment of Zn(II) ion. (b) The 3D supramolecular architecture of 5.
two lattice water molecules. As shown in Fig. 4a, each Zn(II) ion is
six coordinated by a carboxylate oxygen atom from L4ꢁ ligand (Zn–
O 2.0976(18) Å), four nitrogen atoms from two phen molecules,
and one terminal water molecule (Zn–O 2.0673(18) Å), which
forms a slight distorted octahedron. The bond lengths of Ni–N
range from 2.156(2) to 2.210(2) Å, and the distance between two
Zn(II) ions is 19.24 Å in symmetric unit. The bond angles around
Zn(II) center are between 76.89(8)° and 172.00(7)°. The two central
Zn(II) ions are connected each other through a L4ꢁ anion, which
forms a dinuclear structural unit. The carboxylate groups of ligands
show monodentate mode to link two Zn(II) ions (Scheme 1c). Then,
the dinuclear units are combined through the intermolecular
hydrogen bonds, which are composed of water molecules and
uncoordinated carboxylate oxygen atoms and finally formed a 3D
supramolecule (Fig. 4b) (Supporting information, Table S8).
3.6. Thermogravimetric analysis and PXRD
Compounds 1–5 were detected with a heating rate of 5 °C/min
in the range of 25–800 °C under the air atmosphere (Fig. S2). Com-
pound 1–2 maintain a considerable thermal stability up to the
temperature of 360 and 300 °C, respectively. The TGA curve of 1
exhibits that the weight loss above 360 °C stems from the decom-
position of frameworks. For 2, the firstly weight loss is observed
from 300 to 530 °C, which is attributed to the loss of the a phen,
the L4ꢁ ligands are secondly removed from the complex during

M. Yu et al. / Inorganica Chimica Acta 408 (2013) 84–90
89
530–730 °C, with the decomposition of frameworks of 2. For 3, the
first weight loss from 90 to 226 °C is attributed to the loss of coor-
dinated water molecules, it starts to lose H2L2ꢁ ligands as a result
of thermal decomposition above 230 °C and shows the decomposi-
tion of 3. Compound 4 reveals a first weight loss from 30 to 197 °C,
corresponding to the releasing of two lattice and two coordinated
water molecules, and then another four coordinated water mole-
cules and organic L4ꢁ ligands decompose from 220 to 680 °C. Com-
pound 5 gradually loses free waters, coordinated water molecules,
phen and L4ꢁ ligands with increasing temperature, matching with
the fully decomposition above 250 °C (Fig. S2). The results indicate
that the different structures of 1–5 as well as diverse coordination
environment of metal ions have profound effects on the overall
framework rigidity and thermal stability.
In order to check the phase purity of 1, the X-ray powder dif-
fraction (XRPD) pattern was checked at room temperature. As
shown in Fig. S3, most peak positions of simulated and experimen-
tal patterns are in well agreement with each other. And the differ-
ences in intensity may be due to the preferred orientation of the
crystalline powder sample.
Fig. 6. Photoluminescence spectra of 2, 5 and H4L ligand in the solid state at room
temperature.
The least-squares analysis of magnetic susceptibility data leads
to J = ꢁ0.68 cmꢁ1, and g = 2.0. The smaller negative J value suggests
that weak antiferromagnetic interactions between the adjacent
Mn2+ ions.
3.7. Magnetic property
The variable-temperature magnetic susceptibility of 1 is carried
out at an applied field of 1000 Oe in the temperature range of 2–
3.8. Photoluminescence properties
300 K, as shown in the Fig. 5. At 300 K, the experimental vMT value
is 8.56 cm3 K molꢁ1, which is slightly lower than the spin-only va-
As shown in Fig. 6, the emission spectra of the H4L ligand, 2 and
5 were examined in the solid state at room temperature. Emission
of the H4L ligand was observed with a maximum emission peak at
380 nm (kex = 300 nm), which could be attributed to the transition
lue (8.76 cm3 K molꢁ1, S = 5/2) of Mn2+ ions. With lowering the
temperature,
antiferromagnetic interactions of Mn2+ ions in 1. Temperature
dependence of the reciprocal susceptibility (1/ M) well obeys the
vMT value gradually decreases, which indicates an
v
of p⁄ or p⁄? n of the ligand; the photoluminescent peak of
?p
Curie–Weiss law
(v
M = C/(T ꢁ h)) above 8 K with h = ꢁ9.13 K,
phen is located at 381, 416 and 439 nm (kex = 350 nm).[29] 2
exhibits a broad emission band at 434 nm (kex = 382 nm), which
is red-shifted 54 nm in comparing with that of the H4L ligand.
For 5, a broad emission band at 425 nm (kex = 343 nm) was ob-
served, which is red-shifted 45 nm compared with that of the
H4L ligand. These results may be assigned to a ligand-to-metal
charge transfer of 2 and 5 (LMCT).
C = 9.68 cm3K molꢁ1. The negative h value also reveals in the pres-
ence of antiferromagnetic interactions of Mn2+ ions.
The distances between two adjacent Mn2+ ions in a zigzag chain
are 4.2988 and 4.8516 Å, respectively, and the distance of Mn2+
ions between two adjacent chains is 9.8312 Å. Therefore, the mag-
netic interactions of 1 are quantitatively evaluated with similar to
the binuclear Mn(II) complex system [28], the experimental mag-
netic data can be properly fitted using the following equation.
4. Conclusions
2Ng2b2
kT
55e30J=kT þ 30e20J=kT þ 14e12J=kT þ 5e6J=kT þ e2J=kT
11e30J=kT þ 9e20J=kT þ 7e12J=kT þ 5e6J=kT þ 3e2J=kT þ 1
vM
¼
ꢂ
Five transition metal coordination compounds using a semirigid
tetracarboxylic acid have been prepared by the hydrothermal
method. Compounds 1 and 2 are isostructural and exhibit two-
dimensional layered structures. Compound 3 displays a mononu-
clear unit and 4–5 show the dinuclear structures, respectively.
The magnetic property of 1 was exploited, which reveals in the
presence of an antiferromagnetic interactions between Mn(II) ions.
The photoluminescent properties of 2 and 5 were investigated,
which could be assigned to a ligand-to-metal charge transfer.
Acknowledgements
This work is financially supported by the National Natural Sci-
ence Foundation of China (No. 21361017), Inner Mongolia Natural
Science Foundation of China (No. 2012MS0214) and the Scientific
and Technological Key Research Project of Inner Mongolia Colleges
& Universities (NJZZ12012).
Appendix A. Supplementary material
CCDC No. 918037 for 1, 918036 for 2, 918038 for 3, 918039 for
4, 918040 for 5, which can be obtained from the Cambridge Crys-
tallographic Data Centre free of charge via www.ccdc.cam.ac.uk/
data_request/cif. Supplementary data associated with this article
ꢁ1
Fig. 5. Temperature dependence of the
v
MT and vM curve for complex 1.The red
lines represent the best fit to the fitted equation in the text and the Curie–Weiss
law, respectively. (For interpretation of color in Fig. 5, the reader is referred to the
web version of this article.)

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