Syntheses, structures, and fluorescent and magnetic properties of four metal–organic coordination polymers constructed from dicarboxylate ligands

Article abstract of DOI:10.1080/24701556.2020.1862213

Four new coordination polymers, namely [Cd(OBA)(H₂O)₃]_n (1), [Zn₂(OBA)₂(PBHB)₂]_n (2), [Mn(OBA)(BBHB)₂]_n (3), and [Co(MIP)(BPP)]_n (4) (H₂

Full text of DOI:10.1080/24701556.2020.1862213

Inorganic and Nano-Metal Chemistry
ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/lsrt21
Syntheses, structures, and fluorescent and
magnetic properties of four metal–organic
coordination polymers constructed from
dicarboxylate ligands
Yong-Hong Zhou, Yun Xu, Jun-Qing Shi, Yue Su, Mei-Ling Sun, Si-Hui Wang,
Long-Long Wang, Qing-Qing Wang & Yuan-Jie Wei
To cite this article: Yong-Hong Zhou, Yun Xu, Jun-Qing Shi, Yue Su, Mei-Ling Sun, Si-Hui
Wang, Long-Long Wang, Qing-Qing Wang & Yuan-Jie Wei (2021): Syntheses, structures, and
fluorescent and magnetic properties of four metal–organic coordination polymers constructed from
dicarboxylate ligands, Inorganic and Nano-Metal Chemistry, DOI: 10.1080/24701556.2020.1862213
To link to this article: https://doi.org/10.1080/24701556.2020.1862213
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INORGANIC AND NANO-METAL CHEMISTRY
https://doi.org/10.1080/24701556.2020.1862213
Syntheses, structures, and fluorescent and magnetic properties of four
metal–organic coordination polymers constructed from dicarboxylate ligands
Yong-Hong Zhou, Yun Xu, Jun-Qing Shi, Yue Su, Mei-Ling Sun, Si-Hui Wang, Long-Long Wang,
Qing-Qing Wang, and Yuan-Jie Wei
School of Chemistry and Material Science, Huaibei Normal University, Huaibei, P. R. China
ABSTRACT
ARTICLE HISTORY
Received 20 July 2020
Accepted 18 October 2020
Four new coordination polymers, namely [Cd(OBA)(H2O)3]n (1), [Zn2(OBA)2(PBHB)2]n (2),
[Mn(OBA)(BBHB)2]n (3), and [Co(MIP)(BPP)]n (4) (H2OBA ¼ 4-oxyacetate-benzoic acid, PBHB ¼ 1,10-
(1,3-propanediyl)bis-1H-benzimidazole, BBHB ¼ 1,10-(1,4-butanediyl)bis-1H-benzimidazole, H2MIP ¼
5-methylisophthalic acid, and BPP ¼ 1,3-bis(4-pyridyl)propane)), were prepared and structurally
characterized by single-crystal X-ray diffraction. In complex 1, the Cd(II) atoms are bridged by
OBA2ꢀ anions to give 1D zigzag chain, and the 1D chains are stacked into 2D network through
the O–H–O hydrogen bonds. The Mn(II) and Zn(II) centers in 2 and 3 are connected by OBA2ꢀ
anions to form 1D chains, which are further bridged by N-donor ligands to generate 2D layer.
KEYWORDS
Coordination polymer; 4-
oxyacetate-benzoic acid; 5-
methylisophthalic acid;
crystal structure
Complex
4 shows twofold 3D interpenetrating network. Furthermore, the fluorescence
of complexes 1 and 2 and magnetic properties of 3 and 4 have also been investigated.
Introduction
Recently, we have reported a series of CPs constructed
from carboxylate acids and metal ions with the aids of N-
donor ligands.[29–32] As an extension of our work, and to
illustrate the influence of the flexibility and length of the
organic ligands and the metal ions on the architecture and
properties of CPs, we selected H2MIP and H2OBA to react
with Co(II)/Mn(II)/Cd(II)/Zn(II) salts in the presence of
flexible PBHB, BBHB, or BPP ligands under solvothermal or
hydrothermal conditions and obtained four coordination
complexes, [Cd(OBA)(H2O)3]n (1), [Zn2(OBA)2(PBHB)2]n
(2), [Mn(OBA)(BBHB)2]n (3), and [Co(MIP)(BPP)]n (4)
(H2OBA ¼ 4-oxyacetate-benzoic acid, PBHB ¼ 1,10-(1,3-
propanediyl)bis-1H-benzimidazole, BBHB ¼ 1,10-(1,4-buta-
nediyl)bis-1H-benzimidazole, H2MIP ¼ 5-methylisophthalic
acid, and BPP ¼ 1,3-bis(4-pyridyl)propane)), which display
different topological structures and properties. Herein, we
report their syntheses, crystal structures, and fluorescent and
magnetic properties.
In the past few decades, coordination polymers (CPs) have
attracted considerable attention because of their versatile
chemical architectures, easy fabrication, and potential appli-
cations in molecular separation, molecular recognition, mag-
netism, and optoelectronic devices.[1–18] Depending on the
functional groups, lengths and shapes of ligands, and inor-
ganic connecting nodes, the CPs may exhibit various topolo-
gies ranging from chains, channels, pores, interpenetrating
networks to multidimensional frameworks with different
shapes and sizes.[19–21] Nevertheless, it is still a great chal-
lenge to control the fabrication of CPs, as structural modifi-
cations of the organic ligands will play subtle roles in
directing the final architectures through covalent bonding
and/or non-covalent bonding such as hydrogen bonds and
p–p stacking interactions. Therefore, the design and selec-
tion of organic ligands with certain features, such as the
length, flexibility, and functional groups, is critical in obtain-
ing special topology structures. In this context, the explor-
ation of novel organic connectors is an important subject in
coordination chemistry and material science.[22,23]
Frequently, rigid or flexible carboxylate acids are used in the
construction of CPs with diverse topologies due to their
numerous coordination modes, including monodentate, che-
lating, and bridging. Furthermore, the CPs based on main/
transition/lanthanide metal ions and carboxylate acids
ligands can potentially be applied in sensors, separation,
transport of gases, catalysis, and magnetism.[8, 24–28]
Experimental
All starting chemicals were of reagent grade and used as
received. The ligands BBHB and PBHB were synthesized fol-
lowing the literature procedure.[33] Characterization of the
samples was carried out by using FT-IR spectra and elemen-
tal analysis. The FT-IR spectra were performed on Nicolet
170SX FTIR spectrophotometer with KBr pellets within the
400–4000 cmꢀ1 region. Elemental analyses for carbon,
hydrogen, and nitrogen were done with a Vario EL III
CONTACT Yong-Hong Zhou
zhou21921@sina.com
School of Chemistry and Material Science, Huaibei Normal University, Huaibei 235000, P. R. China.
Supplemental data for this article can be accessed https://doi.org/10.1080/24701556.2020.1862213.
ß 2020 Taylor & Francis Group, LLC

2
Y.-H. ZHOU ET AL.
Table 1. Crystal data and structure refinement details for complexes 1–4.
Compound
1
2
3
4
Formula
C9H12CdO8
360.59
C52H44N8O10Zn2
1071.68
C45H44N8O5Mn
831.82
C22H20N2O4Co
435.33
Formula weight
Crystal size (mm3)
0.3 ꢄ 0.28 ꢄ 0.27
0.25 ꢄ 0.22 ꢄ 0.20
0.24 ꢄ 0.23 ꢄ 0.20
0.29 ꢄ 0.25 ꢄ 0.22
Temperature (K)
150
296(2)
296(2)
296(2)
Crystal system
Space group
Monoclinic
P21/c
Monoclinic
Cc
Monoclinic
P21/n
Monoclinic
P21/n
Unit cell dimensions
a(Å)
7.1203(12)
15.8736(12)
9.946(4)
11.0011(12)
b(Å)
16.359(3)
38.815(3)
12.563(5)
11.2802(13)
c(Å)
10.1540(17)
11.2819(8)
90
134.71
90
4940.1(7)
31.646(12)
90
92.947(7)
90
3949(3)
15.8670(18)
a(ꢂ)
90
90
b(ꢂ)
99.712(2)ꢂ
103.543(2)
90
1914.3(4)
c(ꢂ)
90
1165.8(3)
Volume/Å3
Z
4
4
4
4
Density (calculated) (mg/mm3)
2.054
1.905
2.490 to 27.631
712
1.440
1.039
2.395 to 24.996
2204
1.399
0.393
1.289 to 25.00
1740
1.511
0.929
2.05 to 25.00
900
Absorption coefficient (mmꢀ1
)
h range for data collection/(ꢂ)
F(000)
Limiting indices
ꢀ9 ꢅ h ꢅ 7,
ꢀ18 ꢅ h ꢅ 18,
ꢀ46 ꢅ k ꢅ 45, ꢀ13 ꢅ l ꢅ 12
1.026
ꢀ11 ꢅ h ꢅ 11,
ꢀ11 ꢅ k ꢅ 14, ꢀ35 ꢅ l ꢅ 37
1.016
ꢀ13 ꢅ h ꢅ 10,
ꢀ13 ꢅ k ꢅ 9, ꢀ18 ꢅ l ꢅ 18
1.028
ꢀ21 ꢅ k ꢅ 18, ꢀ12 ꢅ l ꢅ 13
Goodness of fit on F2
1.144
Final R indices [I > 2r(I)]
R1 ¼ 0.0221, wR2 ¼ 0.0528
R1 ¼ 0.0359, wR2 ¼ 0.0997
R1 ¼ 0.0633, wR2 ¼ 0.1787
R1 ¼ 0.0397, wR2 ¼ 0.1054
elemental analyzer. The solid state luminescent spectra were the reaction vessel was cooled to room temperature at the
rate of 5 ꢂC/h, colorless block crystals of 3 were collected
with a yield of 34.9 mg, 42%. Elemental analysis (%): calcd
for C45H44N8O5Mn: C 64.92, H 5.29, N 13.46; found C
64.81, H 5.35, N 13.32. IR (cmꢀ1): 3416 m, 1650s, 1535s,
1419s, 1213 m, 859 m, 749 m, 637 m.
taken on a RF-5301PC fluorescence spectrometer at room
temperature. Magnetic susceptibility data of polycrystalline
samples were collected on Quantum Design MPMS SQUZD
magnetometer in the temperature range 2–300 K with an
applied field of 1000 Oe.
½
ð
Þð Þꢃ
Co MIP BPP
:
(4)
n
Synthesis of complexes
A mixture of H2MIP (17.8 mg, 0.1 mmol), BPP (19.8 mg,
0.1 mmol), and Co(OAc)2ꢁ4H2O (24.9 mg, 0.1 mmol) was
dissolved in H2O (10 mL) in a 23-mL Teflon reactor.
Afterward, the reactor was sealed and heated at 120 ꢂC for
3 days and then cooled to room temperature over 36 h. Red
block crystals of 4 suitable for X-ray analysis were obtained
with a yield of 19.6 mg, 45%. Elemental analysis (%): calcd
for C22H20N2O4Co: C 60.64, H 4.59, N 6.43; found C 60.25,
H 4.67, N 6.37. IR (cmꢀ1): 3417 m, 1649s, 1535s, 1421s,
1245s, 1203 m, 865 m, 752 m, 641 m.
Â
Ã
ð
Þ
Cd OBA ðH2OÞ3
:
(1)
n
A mixture of H2OBA (19.6 mg, 0.1 mmol), Cd(OAc)2ꢁ4H2O
(26.6 mg, 0.1 mmol), PBHB (27.6 mg, 0.1 mmol), H2O
(10 mL), and DMF (1 mL) was added to a 23-mL Teflon-
lined vessel, which was sealed and heated at 140 ꢂC for three
days. After the reaction vessel was cooled to room tempera-
ture at the rate of 5 ꢂC/h, colorless needle crystals of 1 were
collected with a yield of 13.7 mg, 38%. Elemental analysis
(%): calcd for C9H12O8Cd: C 29.95, H 3.33; found C 30.15,
H 3.02. IR (cmꢀ1): 3432s, 1612s, 1587s, 1421s, 1409s,
1263 m, 870 m, 769 m, 642 m.
Single crystal structure determination
Â
Ã
ð
Þ ð Þ
Zn2 OBA PBHB
:
(2)
Single-crystal X-ray diffraction data for complexes 1-4 were
obtained on a Bruker Smart Apex-II CCD diffractometer
equipped with Mo Ka radiation (k ¼ 0.71073 Å) by using
u-x scan technique at 296(2) K for 2, 3, and 4 and 150 K
for 1. The structures were solved by direct method and then
refined by full-matrix least-squares technique against F2
using the SHELXTL crystallographic software package.[34]
The non-hydrogen atoms were refined with anisotropic tem-
perature parameters. The hydrogen atoms were placed in
calculated positions and refined using a riding model. A
summary of the crystallographic data and structure refine-
ment details of compounds 1-4 is shown in Table 1.
Selected bond lengths and angles are given in the
2
2
n
Complex 2 was prepared with similar method as 1, using
Zn(OAc)2ꢁ4H2O
(21.9 mg,
0.1 mmol)
instead
of
Cd(OAc)2ꢁ4H2O, and the pale yellow block crystals of 2
were obtained with a yield of 23 mg, 43%. Elemental analysis
(%): calcd for C52H44N8O10Zn2: C 58.22, H 4.10, N 10.45;
found C 58.61, H 4.25, N 10.72. IR (cmꢀ1): 3411 m, 1655s,
1539s, 1421s, 1218 m, 865 m, 751 m, 639 m.
Â
Ã
ð
Þð Þ
Mn OBA BBHB
:
(3)
2
n
A
mixture of H2OBA (19.6 mg, 0.1 mmol), BBHB
(29.0 mg, 0.1 mmol), Mn(OAc)2ꢁ4H2O (24.5 mg, 0.1 mmol),
and H2O (10 mL) was added to a 23-mL Teflon-lined vessel,
which was sealed and heated at 130 ꢂC for three days. After Supporting Information (Table S1).

INORGANIC AND NANO-METAL CHEMISTRY
3
Figure 1. (a) The coordination environment of Cd(II) center in 1 (thermal ellip-
soids are drawn at 30% probability), (b) the 1D chain structure formed by Cd(II)
atoms and OBA2ꢀ anions in 1, and (c) the 2D supramolecular assembly formed
through O–H–O hydrogen bond interactions.
Results and discussion
Description of crystal structures
Figure 2. (a) The coordination environment of Zn(II) center in 2 (thermal ellip-
soids are drawn at 30% probability), (b) the 1D chain structure formed by Zn (II)
atoms and OBA2ꢀ anions in 2, and (c) the 2D layer formed by the 1D chains
and PBHB ligands in 2.
Â
Ã
ð
Þ
Cd OBA ðH2OÞ3
:
(1)
n
In 1, the asymmetric unit consists of one Cd(II) atom, one
OBA2ꢀ ligand, and three coordinated water molecules. As
shown in Figure 1(a), the Cd(II) atom locates in a distorted
pentagonal bipyramidal geometry which contains four O
atoms from two different OBA2ꢀ anions with chelating
mode and three O atoms from the coordinated water mole-
cules. The O1B, O2B, O4, O5, and O7 atoms make up the
containing O4 and O5 atoms is almost coplanar to the phe-
nyl ring with dihedral angle of 2.9ꢂ, while the flexible carb-
oxyl group containing O1 and O2 atoms is nearly
perpendicular to the phenyl ring with dihedral angle of
80.1ꢂ. The adjacent Cd(II) atoms are bridged by the OBA2ꢀ
anions to generate an infinite 1D zigzag chain along the b-
equatorial plane, whereas the O6 and O8 atoms are in the axis with the Cd–Cd separation of 10.27 Å (Figure 1(b)).
axial positions with the O6-Cd-O8 angle of 168.42(6)ꢂ. The
Cd–O bond lengths are in the range of 2.2639(18)-
2.4403(17) Å, which are in the normal ranges for the related
Cd(II) CPs.[35,36] The OBA2ꢀ ligand shows remarkable flexi-
bility as demonstrated by the angles between the carboxyl
groups and the benzene ring. The rigid carboxyl group
Furthermore, the 1D chains are stacked into 2D network on
the bc plane through the O–H–O hydrogen bonds between
the coordinated water molecules and the carboxyl groups, as
shown in Figure 1(c).
Â
Ã
ð
Þ ð Þ
Zn2 OBA PBHB
:
(2)
2
2
n

4
Y.-H. ZHOU ET AL.
Scheme 1. The conformations of BBHB in complex 3.
Figure 3. (a) The coordination environment of Mn(II) center in 3 (thermal ellip-
soids are drawn at 30% probability), (b) the 1D zigzag chain in 3, and (c) view
of the 2D layer formed by the 1D chains and BBHB ligands in 3.
rings of 58.23ꢂ, connecting the 1D chains to 2D framework
with the interchain separation of 11.28 Å (Figure 2(c)).
Â
Ã
Complex 2 crystallizes in monoclinic system with space
group Cc. There are two crystallographically independent
Zn(II) centers with different coordination geometries in the
asymmetric unit. As illustrated in Figure 2(a), Zn1 ion lies in a
distorted trigonal bipyramidal coordination sphere, as indexed
by the s value of 0.72 [s ¼ (x1-x2)/60, where x1 and x2 are the
largest angles around the metal center, s ¼ 0 for a perfect
square pyramid and 1 for a perfect trigonal bipyramid],[37]
which is formed by three O atoms from two OBA2ꢀ anions,
and two N atoms of two different PBHB ligands. Zn2 center is
located in tetrahedral coordination environment, being bound
to two O atoms from two OBA2ꢀ anions and two N atoms
from two PBHB molecules. The Zn–O/N bond distances are in
the normal ranges. Each fully deprotonated OBA2ꢀ ligand is
coordinated to two Zn(II) ions by one rigid chelating carboxyl-
ate and one flexible monodentate carboxylate and thereby acts
as a bis-connecting ligand. The coordination fashions of the
carboxyl groups are different from that observed in complex 1.
Along the b-axis, the Zn1 and Zn2 ions are arranged alterna-
tively, bridged by the OBA2ꢀ ligands to give the formation of
1D chain with the Zn–Zn separation of 10.30 Å (Figure 2(b)).
The PBHB ligands assume TG (T ¼ trans, G ¼ gauche) con-
ð
Þð Þ
Mn OBA BBHB
:
(3)
2
n
Single-crystal X-ray diffraction study reveals that 3 is
monoclinic with P21/n space group. The asymmetric unit
consists of one Mn(II) ion, one OBA2ꢀ ligand, and two
BBHB ligands. As shown in Figure 3(a), the Mn(II) ion is
six coordinated by three O atoms from two OBA2ꢀ ligands
and three N atoms from three BBHB molecules, resulting in
a distorted octahedral coordination environment. The dis-
tances of Mn–O and Mn–N bonds span the range of
2.118(3)–2.279(3) and 2.209(3)-2.318(3) Å, which are com-
parable with those reported in other Mn(II) complex.[38]
The OBA2ꢀ ligand serves as bis-connector through its two
carboxylate moieties in chelating and monodentate modes,
respectively, bridging the adjacent Mn(II) ions to form 1D
zigzag chain with the Mn–Mn separation of 11.43 Å (Figure
3(b)). The Mn–Mn distance is somewhat longer than that
reported in [Mn(MIP)(2,2-bipy)(H2O)]n.[38] It should be
pointed out that there are two independent sets of BBHB
spacers (Scheme 1). For the one set to which N1 and N2
belongs, the BBHB ligand adopts GTT conformation with
the dihedral angle between the two imidazole rings of
87.29ꢂ, whereas the set to which N5 and N8 belongs exhibits
formation with the dihedral angle between two benzimidazole TGG conformation with the dihedral angle between the two

INORGANIC AND NANO-METAL CHEMISTRY
5
Figure 4. (a) The coordination environment of Co(II) center in 4 (thermal ellipsoids are drawn at 30% probability), (b) the 1D chain structure formed by Co(II) atoms
and MIP2ꢀ anions in 4, (c) the 2D layer structure formed by the 1D chains and the BPP ligands, (d) the 3D meal–organic framework in 4, and (e) the twofold inter-
penetrated network of 4.
imidazole rings of 87.52ꢂ. The BBHB ligand with GTT con- Co(II) center is shown in Figure 4(a). The asymmetric unit
formation that exhibits monodentate mode with one pyri- of 4 contains one Co(II) atom, one MIP2ꢀ anion, and one
BPP ligand. The Co(II) atom is four coordinated by two N
atoms from two BPP ligands and two O atoms from two
MIP2ꢀ anions, locating in a tetrahedral geometry. The
Co–N bond distances are 2.050(2) and 2.060(2) Å, which
are comparable with those found in {[Co(BPP)(OH-
BDC)]ꢁH2O}n (OH-H2BDC ¼ 5-hydroxyisophthalic acid)[39]
and [Co3(boaba)2(4,4-bipy)2(H2O)8] (H3boaba ¼ 3,5-bis-
dine moiety does not participate in the coordination. As for
the BBHB ligands with TGG conformation, they establish a
physical bridge between the neighboring 1D chains, con-
structing a 2D infinite layer framework with the interchain
distance of 9.95 Å (Figure 3(c)).
½
ð
Þð Þꢃ
Co MIP BPP
:
(4)
n
Complex 4 crystallizes in monoclinic form with P21/n oxyacetate-benzoic acid, 4,4-bipy ¼ 4,4-bipyridine).[40] The
space group, and the coordination environment around the Co–O bond lengths are 1.969(2) and 1.967(2) Å, which are

6
Y.-H. ZHOU ET AL.
Figure 6. Temperature dependences of vMT and vM for 3.
Figure 5. The fluorescence spectra of 1 and 2 in the solid state at room
temperature.
much shorter than those reported in [Co(OH-BDC)
(BPP)0.5(H2O)]n.[41] The fully deprotonated H2MIP ligand
shows the bis-monodentate coordination fashions for the
two carboxyl groups, and the symmetry-related Co(II) atoms
are bridged by two bis-monodentate carboxyl groups to
form a 1D polymeric chain with the Co–Co separation of
17.06 Å (Figure 4(b)). The BPP ligand adopts TG conform-
ation with the dihedral angle between two terminal benzene
rings of 76.41ꢂ, progressing the adjacent 1D chains to yield
2D infinite layer framework (Figure 4(c)). The resulting 2D
structure is further cross-linked by BPP ligands, giving rise
to the formation of a 3D porous supramolecular architecture
(Figure 4(d)). The single 3D network possesses channels
of sizes 12.83 ꢄ 9.49 Å2. In order to diminish the void
cavities and stabilize the whole framework, the potential
Figure 7. Temperature dependences of vMT and vM for 4.
voids are effectively accommodated through interpenetration properties of complex 1 and 2 were investigated at room
of another independent equivalent framework, generating temperature. As displayed in Figure 5, the emission spectra
a twofold interpenetrated architecture, which is similar to exhibit the main peaks at 438 nm for 1 and 429 nm for 2.
those reported in [Co(pbc)2(H2O)]n (Hpbc ¼ 3-Pyrid-4-
Comparatively, H2OBA shows an intense emission peak at
ylbenzoic acid)[42] and [Zn(FA)(bmix)0.5]nꢁnH2O (H2FA ¼
397 nm. Presumably, the emissions of complexes 3 and 4
may be attributed to the intraligand p–p transition.[46,47]
ꢆ
fumaric acid, bmix ¼ 1,4-bis(2-methyl-1H-imidazol-1-ylme-
thyl)benzene).[43] The final effective cavities are 2.5% of the
unit cell volume upon interpenetration. Ma and coworkers
have previously reported one Co(II) CP {[Co(MIP)(BPP)]}n
(I) based on H2MIP and BPP ligands.[44] Though I and 4
share the same formula, they exhibit quite different struc-
tural features. In I, the two carboxyl groups adopt chelating
and bidentate bridging modes, linking two Co(II) ions to
form binuclear structure. These binuclear subunits are
further bridged by MIP2ꢀ ligands to form 1D polymeric
ribbon, which is further packed to a 2D supramolecular
layer by the C–H–p interactions.
The red shifts of the bands compared to that of the free
H2OBA should be ascribed to the coordination of the
ligands to the Zn(II) or Cd(II) centers.
The temperature dependence of magnetic susceptibilities
of 3 and 4 was measured from 2 to 300 K with a 1000 Oe
applied magnetic field. The vM and vMT versus T curves for
3 and 4 are given in Figures 6 and 7, respectively. As
depicted in Figure 6, the vMT value is 4.51 cm3 molꢀ1 K at
300 K. Along with the decreasing temperature, the vMT val-
ues increase slowly to maximum value of 6.05 cm3 molꢀ1
K
at 26 K, andꢀt1hen it decreases rapidly to 4.25 cm3 molꢀ1 K at
2 K. The vM as a function of T is linear in the temperature
range 2–300 K, obeying the Curie–Weiss law with
C ¼ 4.49 cm3 molꢀ1 and h ¼ 13.15 K. The results suggest the
presence of ferromagnetic interactions between the adjacent
Mn(II) centers. Compared with 3, the vMT versus T curve
Photoluminescent and magnetic properties
Previous studies have revealed that CPs constructed from
d10 metal centers and organic ligands have shown potential
applications in chemical sensors, photochemistry, and of complex 4 shows different features. As shown in
light-emitting diodes.[45] Thus, the solid-state luminescent Figure 7, the vMT value is 2.15 cm3 molꢀ1 K at room

INORGANIC AND NANO-METAL CHEMISTRY
7
Anorg. Allg. Chem. 2017, 643, 1801–1808. DOI: 10.1002/zaac.
201700344.
temperature for 4. Upon cooling, the vMT values decrease
continuously to reach minimum value of 0.40 cm3 molꢀ1
K
7. Wang, P.; Fan, R. Q.; Yang, Y. L.; Liu, X. R.; Xiao, P.; Li, X. Y.;
Hasi, W.; Cao, W. W. 1-D Helical Chain, 2-D Layered Network
and 3-D Porous Lanthanide-Organic Frameworks Based on
Multiple Coordination Sites of Benzimidazole-5, 6-Dicarboxylic
Acid: synthesis, Crystal Structure, Photoluminescence and
Thermal Stability. CrystEngComm 2013, 15, 4489–4506. DOI:
10.1039/c3ce40184g.
ꢀ1
at 2 K. Between 2 and 300 K, the vM versus T data follow
the Curie–Weiss law, vM ¼ C/(T-h) with C ¼ 2.03 cm3
molꢀ1 and h ¼ ꢀ9.55 K. The negative h value indicates the
occurrence of antiferromagnetic interactions between the
Co(II) ions.
8. Bu, F.; Lin, Q. P.; Zhai, Q. G.; Wang, L.; Wu, T.; Zheng, S. T.;
Bu, X. H.; Feng, P. Y. Two zeolite-type frameworks in one
metal-organic framework with Zn24 @Zn104 cube-in-sodalite
architecture. Angew. Chem. Int. Ed. Engl. 2012, 51, 8538–8541.
DOI: 10.1002/anie.201203425.
Conclusions
Four metal–organic CPs have been successfully isolated
under solvothermal or hydrothermal conditions by the reac-
tions of dicarboxylate ligands with Zn(II)/Cd(II)/Mn(II)/
Co(II) salts in the presence of different N-donor ligands.
The results of this work further illustrate the H2OBA and
H2MIP are good candidates for the construction of CPs due
to their versatile coordination modes. Combined with the
varied conformations of N-donor ligands, it is believed that
the mixed-ligands self-assembly strategy of carboxylate and
N-containing auxiliary ligands can offer perspectives to the
rational preparation of CPs with specific structures
and properties.
9. Liu, D.; Lang, J. P.; Abrahams, B. F. Highly Efficient
Separation of a Solid Mixture of Naphthalene and Anthracene
by
a Reusable Porous Metal-Organic Framework through
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Soc. 2011, 133, 11042–11045. DOI: 10.1021/ja203053y.
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Functional Molybdenum (Tungsten)-Copper-Sulfur Coordination
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Chem. Soc. Rev. 2016, 45, 4995–5019. DOI: 10.1039/c6cs00096g.
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Wang, H. F.; Lang, J. P. Coordination-Driven Stereospecific
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Yin, S. G. Fine-Tuning Ligand to Modulate the Magnetic
Funding
Anisotropy in
a Carboxylate-Bridged Dy2 Single-Molecule
This work was financially supported by Scientific Research
Foundation of Anhui Provincial Education Department
(KJ2019A0597, KJ2020A0022) and Teaching Quality and
Magnet System. Inorg. Chem. 2016, 55, 5578–5584. DOI:
10.1021/acs.inorgchem.6b00653.
13. Zhou, L. J.; Deng, W. H.; Wang, Y. L.; Xu, G.; Yin, S. G.; Liu,
Q. Y. Lanthanide-Potassium Biphenyl-3,3’-disulfonyl-4,4’-
dicarboxylate Frameworks: Gas Sorption, Proton Conductivity,
and Luminescent Sensing of Metal Ions. Inorg. Chem. 2016, 55,
6271–6277. DOI: 10.1021/acs.inorgchem.6b00928.
Teaching
Reform
Project
of
Huaibei
Normal
University (JY18022).
14. Li, Y. J.; Wang, Y. L.; Liu, Q. Y. The Highly Connected MOFs
Constructed from Nonanuclear and Trinuclear Lanthanide-
Carboxylate Clusters: selective Gas Adsorption and Luminescent
pH Sensing. Inorg. Chem. 2017, 56, 2159–2164. DOI: 10.1021/
acs.inorgchem.6b02811.
15. Li, R. P.; Liu, Q. Y.; Wang, Y. L.; Liu, C. M.; Liu, S. J. Evolution
from Linear Tetranuclear Clusters into One-Dimensional Chains
of Dy(III) Single-Molecule Magnets with an Enhanced Energy
Barrier. Inorg. Chem. Front. 2017, 4, 1149–1156. DOI: 10.1039/
C7QI00178A.
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