Metal-dependent structural variations based on mixed ligands of 5-hydroxy isophthalic acid and 1,3-bis(imidazol-1-ylmethyl)benzene: Solvothermal syntheses, structural characterizations, luminescence and magnetic properties

Article abstract of DOI:10.1016/j.ica.2015.10.033

Three 5-hydroxy isophthalic acid (H₂OIP) based coordination polymers, namely, {[Cu(OIP)(bimb)]·H₂O}_n (1), {[Co₂(OIP)₂(bimb)₂]·H₂O}_n (2), and [Zn(OIP)(bimb)]_n

Full text of DOI:10.1016/j.ica.2015.10.033

Accepted Manuscript
Metal-Dependent Structural Variations Based on Mixed Ligands of 5-Hydroxy
Isophthalic Acid and 1,3-Bis(imidazol-1-ylmethyl)benzene: Solvothermal Syn-
theses, Structural Characterizations, Luminescence and Magnetic Properties
Xiutang Zhang, Liming Fan, Weiliu Fan, Xian Zhao
PII:
S0020-1693(15)00527-7
http://dx.doi.org/10.1016/j.ica.2015.10.033
ICA 16743
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
27 May 2015
4 October 2015
16 October 2015
Please cite this article as: X. Zhang, L. Fan, W. Fan, X. Zhao, Metal-Dependent Structural Variations Based on
Mixed Ligands of 5-Hydroxy Isophthalic Acid and 1,3-Bis(imidazol-1-ylmethyl)benzene: Solvothermal Syntheses,
Structural Characterizations, Luminescence and Magnetic Properties, Inorganica Chimica Acta (2015), doi: http://
dx.doi.org/10.1016/j.ica.2015.10.033
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

For Table of Contents Use Only
Table of Contents Graphic and Synopsis
Metal-Dependent Structural Variations Based on Mixed Ligands of 5-Hydroxy
Isophthalic Acid and 1,3-Bis(imidazol-1-ylmethyl)benzene: Solvothermal Syntheses,
Structural Characterizations, Luminescence and Magnetic Properties
Xiutang Zhang (X. Zhang), Liming Fan (L. Fan), Weiliu Fan (W. Fan), and Xian Zhao (X. Zhao)
Highlights:
ꢀ
ꢀ
Three new coordination polymers were synthesized and characterized.
The mixed ligands strategy of 5-hydroxy isophthalic acid and 1,3-bis(imidazol-1-ylmethyl)benzene ligands were
introduced to design coordination polymers.
ꢀ
Metal ions coordination preferences play important roles in determining the three coordination polymers.
The structural diversity, magnetic and photoluminescence properties were also discussed.
ꢀ

Pictogram: The coordination preferences of different metal ions in synthetic procedures of the three mixed ligands
based coordination polymers.

_____________________________________________________________________
Contents lists available at SciVerse ScienceDirect
Inorganic Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Metal-Dependent Structural Variations Based on Mixed Ligands of 5-
Hydroxy Isophthalic Acid and 1,3-Bis(imidazol-1-ylmethyl)benzene:
Solvothermal Syntheses, Structural Characterizations, Luminescence
and Magnetic Properties
Xiutang Zhang,*a,b Liming Fan,a,b Weiliu Fan,b and Xian Zhao*b
a Advanced Material Institute of Research, College of Chemistry and Chemical Engineering, Qilu Normal University,
Jinan, 250013, China. E-mail: xiutangzhang@163.com;
b
State Key Laboratory of Crystal Materials, Shandong University , Jinan 250100, China. E-mail:
xianzhao@sdu.edu.cn.
Keywords: 5-Hydroxy isophthalic acid, 1,3-Bis(imidazol-1-ylmethyl)benzene,
Coordination preference,
Luminescent property, Magnetic property
1

Inorganic Chimica Acta Volume (2015) Page
ABSTRACT
Three 5-hydroxy isophthalic acid (H2OIP) based coordination polymers, namely, {[Cu(OIP)(bimb)]•H2O}n (1),
{[Co2(OIP)2(bimb)2]•H2O}n (2), and [Zn(OIP)(bimb)]n (3) were synthesized under hydrothermal conditions in the
presence of bis(imidazole) bridging linkers (bimb = 1,3-bis(1H-imidazol-4-yl)benzene) (bimb)). Their structures have
been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR
spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complex 1 displays a 3D ABAB
packing supramolecular structure with 4-connected 2D wave sql sheet. Complex 2 possesses a 3D 5-connected bnn
net based on [Co2(COO)2] secondary building unit (SBU) with a Schlä
fli symbol of (46•64). Complex 3 features a 2D
flat sql net with Zn ions as 4-connected nodes. Moreover, the magnetic property of complex 2 and the solid state
luminescence of complex 3 have been investigated.
2

_____________________________________________________________________
Contents lists available at SciVerse ScienceDirect
Inorganic Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Metal-Dependent Structural Variations Based on Mixed Ligands of 5-
Hydroxy Isophthalic Acid and 1,3-Bis(imidazol-1-ylmethyl)benzene:
Solvothermal Syntheses, Structural Characterizations, Luminescence
and Magnetic Properties
Xiutang Zhang,*a,b Liming Fan,a,b Weiliu Fan,b Xian Zhao*b
a
Advanced Material Institute of Research, College of Chemistry and Chemical Engineering, Qilu Normal University, Jinan, 250013,
China.
b State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China.
______________________________________________________________________________________________________________
ABSTRACT: Three 5-hydroxy isophthalic acid (H2OIP) based coordination polymers,
namely, {[Cu(OIP)(bimb)]•H2O}n (1), {[Co2(OIP)2(bimb)2]•H2O}n (2), and
[Zn(OIP)(bimb)]n (3) were synthesized under hydrothermal conditions in the presence of
bis(imidazole) bridging linkers (bimb = 1,3-bis(1H-imidazol-4-yl)benzene) (bimb)).
Their structures have been determined by single-crystal X-ray diffraction analysis and
further characterized by elemental analysis, IR spectra, powder X-ray diffraction (PXRD),
and thermogravimetric (TG) analysis. Complex 1 displays a 3D ABAB packing
supramolecular structure with 4-connected 2D wave sql sheet. Complex 2 possesses a 3D
5-connected bnn net based on [Co2(COO)2] secondary building unit (SBU) with a
ARTICLEINFO
Aritcle history:
Received 01 January 2015
Received in revised form
01 January 2015
Accepted 01 January 2015
Available online 01 January 2015
Keywords:
5-Hydroxy isophthalic acid
1,3-bis(1H-imidazol-4-yl)benzene)
Coordination preference
Luminescent property
Magnetic property
Schlä
fli symbol of (46•64). Complex 3 features a 2D flat sql net with Zn ions as 4-
connected nodes. Moreover, the magnetic property of complex 2 and the solid state
luminescence of complex 3 have been investigated.
_____________________________________________________________________________________________________________________________________________________________________
materials are always dependent on many uncertain factors,
such as the coordination geometry preferred by the metal,
solvent systems, templates, pH values, counteranions, and
the chemical structures of the selected ligands [7-12].
Among these factors, the rational selection of the
characteristic ligand proved to be one efficient route for the
construction of versatile CPs. Generally, the length, rigidity,
coordination modes, and functional groups or substituents
of polycarboxylate ligands have consequential effects on the
final structures of CPs [13]. Moreover, a recent study on
coordination assemblies using (bis)imidazole linkers as
ancillary ligands provided a reliable strategy for obtaining
new topological prototypes of coordination nets [14]. The
ancillary ligands have a great effect on the coordination
modes of the host polycarboxylate aromatic acid and the
final packing structures. With the length of the ancillary
ligands increasing, the longer separation of neighboring
central ions makes the host aromatic polycarboxylate ligand
adopt more “open” coordination modes and the overall
structure a higher degree of interpenetration. The greater
1. Introduction
Functional coordination polymers (CPs), a class of novel solid
materials, have attracted thousands of coordination chemists
and engineers for their interesting structures as well as potential
applications in gas separation and storage, catalysis, magnetism,
optical properties, and microelectronics sensing [1–4]. The
architectures and functions of these materials can be tailored by
altering factors such as the metal cations, solvent media,
templating agent, pH, counteranion, and the chemical structure
of organic ligands [5–7]. Strategically designed or select
featured organic ligands according to their length, rigidity,
coordination modes, and functional groups or substituents were
proved to be an efficient route for achieving the expected CPs
[8].
However, the controllable synthesis of prospective
networks is still a far-reaching challenge since such
*Corresponding author.
E-mail
address:
xiutangzhang@163.com
(X.
Zhang);
xianzhao@sdu.edu.cn (X. Zhao).
3

Inorganic Chimica Acta Volume (2015) Page
2.2. Syntheses
flexibility of ancillary ligands could make the final structure
more twisted and complicated [15]. Thus, CPs can be
assembled from predetermined organic building blocks
through judicious selection of ligands and careful control of
reaction conditions. To the best of our knowledge, CPs
based on 5-hydroxy isophthalic acid (H2OIP) in the
presence of 1,3-bis(1H-imidazol-4-yl)benzene) (bimb) have
never been documented to date [16-19]. On the other hands,
the mixed-ligand strategy has been proved to be efficient in
the assembly of numerous CPs [20-27]. Compared to the
ordinary cheating N-donors, such as the 2,2-bipyridine
(bpy), and phenanthroline (phen), it is no doubt that the 1,3-
bis(1H-imidazol-4-yl)benzene) (bimb) could be employed
to construct high-dimension CPs more easily due to that the
flexible backbones of the bimb can adjust itself to
coordinate with metal ions by twisting, rorating, folding,
and so on [28-30].
Thus, these considerations inspired us to explore new
coordination frameworks with 5-hydroxy isophthalic acid
(H2OIP) and 1,3-bis(1H-imidazol-4-yl)benzene) (bimb),
shown in Scheme 1). Herein, we reported the syntheses and
characterizations of three new coordination polymers,
{[Cu(OIP)(bimb)]·H2O}n (1), {[Co2(OIP)2(bimb)2]·H2O}n
(2), and [Zn(OIP)(bimb)]n (3), which exhibit a systematic
variation of architectures from 2D flat sql net, 2D wave sql
net, to 3D (46·64)-bnn net. Structural comparisons indicated
that the metal ions are crucial factors for in determining the
structural diversity of coordination polymers. In addition,
the magnetic property of complex 2 and the solid state
luminescence of complex 3 have been investigated.
2.2.1. Preparation of {[Cu(OIP)(bimb)]·H2O}n (1)
A mixture of H2OIP (0.30 mmol, 0.055 g), bib (0.30 mmol,
0.071 g), CuSO4·5H2O (0.30 mmol, 0.075 g), NaOH (0.30
mmol, 0.012 g), 6 mL H2O and 3 mL CH3CN was sealed in a
25 mL Teflon-lined stainless steel vessel, which was heated to
150 °C for 3 days and then cooled to 25 °C at a rate of 10 °C
h−1. Blue block crystals of 1 were obtained with the yield of 47
% (based on Cu). Anal. (%) calcd. for C22H20CuN4O6: C,
52.85; H, 4.03; N, 11.21. Found: C, 52.71; H, 4.26; N, 10.98.
IR (KBr pellet, cm-1): 3486 (m), 3096 (m), 1683 (s), 1569 (s),
1421 (vs), 1121 (m), 897 (w), 838 (m), 753 (w).
2.2.2. Preparation of {[Co2(OIP)2(bimb)2]·H2O}n (2)
The same synthetic procedure as for 1 was used except that
CuSO4·5H2O was replaced by CoSO4·7H2O, giving purple
block crystals. The precipitate that formed was collected by
filtration, and dried at room temperature to give 2 in 53 % yield
based on Co. Anal. (%) calcd. for C44H38Co2N8O11: C, 54.33;
H, 3.94; N, 11.52. Found: C, 53.96; H, 4.10; N, 11.38. IR (KBr
pellet, cm-1): 3451 (m), 3121 (w), 1748 (m), 1623 (vs), 1461
(s), 1276 (w), 1147 (s), 857 (m), 776 (m).
2.2.3. Preparation of [Zn(OIP)(bimb)]n (3)
The same synthetic procedure as for 1 was used except that
CuSO4·5H2O was replaced by ZnSO4·7H2O, giving colourless
block crystals. The precipitate that formed was collected by
filtration, and dried at room temperature to give 3 in 61 % yield
based on Zn. Anal. (%) calcd. for C11H9N2O2.5Zn0.5: C, 54.62;
H, 3.75; N, 11.58. Found: C, 54.45; H, 3.89; N, 11.36. IR (KBr
pellet, cm-1): 3457 (m), 3130 (w), 1787 (w), 1693 (vs), 1548
(s), 1486 (s), 1321 (m), 996 (m), 913 (m), 756 (m).
2.3. X-ray crystallography
Single crystals of the complexes 1–3 with appropriate
dimensions were chosen under an optical microscope and
quickly coated with high vacuum grease (Dow Corning
Corporation) before being mounted on a glass fiber for data
collection. Intensity data collection was carried out on a
Siemens SMART diffractometer equipped with a CCD detector
using MoKα monochromatized radiation (λ = 0.71073 Å) at
296(2) K. The absorption correction was based on multiple and
symmetry-equivalent reflections in the data set using the
SADABS program. The structures were solved by direct
methods and refined by full-matrix least-squares using the
SHELXTL package [31]. Anisotropic thermal parameters were
applied to all non- hydrogen atoms. And all hydrogen atoms
attached to C and N atoms were placed geometrically [32].
Crystallographic data for complexes 1–3 are given in Table 1.
Selected bond lengths and angles for 1–3 are listed in Table S1.
Scheme 1. The organic ligands in the assembly of titled complexes.
2. Experimental
2.1. Materials and Methods
All the chemical reagents were purchased from Jinan
Henghua Sci. & Tec. Co. Ltd. without further purification.
Elemental analyses of C, N, and H were performed on an
EA1110 CHNS-0 CE elemental analyzer. IR (KBr pellet)
spectra were recorded on a Nicolet Magna 750FT-IR
spectrometer. Thermogravimetric measurements were
carried out in a nitrogen stream using a Netzsch STA449C
o
apparatus with a heating rate of 10 C min–1. X-Ray powder
diffraction (XRPD) was carried out on
a RIGAKU
DMAX2500 apparatus. Fluorescent data were collected on
an Edinburgh FLS920 TCSPC system. Fluorescent data
were collected on an Edinburgh FLS920 TCSPC system.
Table 1 Crystal data for 1-3
Complex
Formula
Mr
1
2
3
C22H20CuN4O6 C44H38Co2N8O11 C11H9N2O2.5Zn0.5
499.96
The
variable-temperature
magnetic
susceptibility
972.68
241.89
measurements were performed on the Quantum Design
SQUID MPMS XL-7 instruments in the temperature range
of 2-300 K under a field of 1000 Oe.
Crystal system Monoclinic
Monoclinic
P21/n
9.9842(4)
34.3888(17)
Monoclinic
P21/n
10.8851(4)
16.5714(6)
Space group
a (Å)
P21/n
10.1050(11)
19.2546(19)
b (Å)
4

the CuII ions, forming a 1D straight [Cu(bimb)]n chain with the
adjacent CuII ions distance is 11.132 Å (Fig. S2). Sharing with
the CuII centers, a 2D sheet was constructed (Fig. 2). The
neighboring sheets packed with each other with ABAB
arrangement through the hydrogen bonds interaction
[O5−H5···O3i = 2.600 Å, Symmetry code: i: x+1/2, -y+3/2,
z+1/2.], finally given a 3D supramolecular structure (Fig. 3).
Besides, hydrogen bonds [O1w−H2w···O5ii = 2.854 Å,
O1w−H1w···O4iii = 3.021 Å, Symmetry codes: ii: x-1/2, -y+3/2,
z-1/2; iii: -x+3/2, y-1/2, -z+3/2.] between lattice water
molecules and the sheets also play important roles in
maintaining the stability of the supramolecular architecture.
From the viewpoint of topology [33], the final structure of 1
can be defined as sql sheet. If we take the hydrogen bonds into
consideration, the 3D supramolecular frameworks can be
simplified to be a 6-connected pcu net (Fig. 4).
c (Å)
11.1318(11)
91.590(3)
2165.1(4)
4
1.534
1.057
296(2)
1028
0.0643
R1 = 0.0418
wR2 = 0.0944
R1 = 0.0646
wR2 = 0.1057
1.001
11.8547(5)
99.7390(10)
4011.6(3)
4
1.611
0.904
296(2)
2000
0.0714
R1 = 0.0407
wR2 = 0.0907
R1 = 0.0693
wR2 = 0.1033
0.999
12.0802(4)
112.7180(10)
2009.98(12)
8
1.599
1.267
296(2)
992
0.0469
R1 = 0.0285
wR2 = 0.0574
R1 = 0.0352
wR2 = 0.0608
0.999
β (°)
V (Å3)
Z
ρ (g cm–3)
µ (mm-1)
T (K)
F(000)
Rint
R [I > 2σ(I)]a
R (all data)a
Gof
CCDC number 1402562
1402563
1402625
aR1 = Σ| |Fo|−|Fc| |/ Σ|Fo|, wR2 = [Σw(Fo2−Fc2)2]/ Σw(Fo2)2]1/2
3. Result and discussion
3.1. Descriptions of crystal structures
Figure 1. The asymmetric unit of complex 1 (Symmetry codes: B: x, y,
1+z; C: 1/2−x, −1/2+y, 3/2−z).
Figure 3. The 3D supramolecular structure of complex 1 by ABAB
sheets packing.
Figure 2. The 2D flat [Cu(OIP)(bimb)] sheet containing the 1D
[Cu(bimb)]n and 1D [Cu(OIP)]n chains.
Figure 4. The pcu topology for the 3D supramolecular structure of
complex 1.
3.1.1. {[Cu(OIP)(bimb)]·H2O}n (1)
The single-crystal X-ray diffraction analysis reveals that
complex 1 crystallizes in the monoclinic system, P21/n space
group, and the asymmetric unit of 1 consists of one CuII ion,
one OIP2- ligand, one bimb ligand, and one lattice water
molecule. As shown in Fig. 1a, the CuII center locates in a
distorted octahedral geometry, coordinated by four O atoms
from two different OIP2- ligandsand two N atoms from two
distinct bimb ligands, and the angles around it fall in the range
of 89.38(10)−160.70(8)º.
3.1.2. {[Co2(OIP)2(bimb)2]·H2O}n (2)
Single-crystal X-ray diffraction analysis reveals that
complex 2 crystallizes in the monoclinic system, P21/n space
group, and the asymmetric unit of 2 consists of two CoII ions,
two OIP2- ligands, two bimb ligands, and one lattice water
molecule. As illustrated in Fig. 5, Co(1) is located at a general
center with a trigonal bipyramidal geometry surrounded by
three O atoms from three different OIP2- ligands occupying the
basal positions [Co(1)–O(1) = 2.001(2) Å, Co(1)–O(7) =
2.049(2) Å, and Co(1)–O(9)D = 2.011(2) Å] and two N atoms
forming the apical positions [Co(1)–N(1) = 2.119(3) Å, and
Co(1)–N(7) = 2.134(3) Å]. Co(2) is located in a similar
The OIP2- ligand act as bridging linker to bind two CuII ions
through two (κ1-κ1) cheating carboxyl groups, leaving a 1D flat
[Cu(OIP)]n chains with the neighboring CuII distances being
10.006 Å (Fig. S1). Along the other direction, the bimb bridged
5

Inorganic Chimica Acta Volume (2015) Page
[CoN2O3] trigonal bipyramidal geometry, coordinated by three
It is noteworthy that the unprecedented [Co(bimb)]n chains
with right- and left-handed chiral characteristics were built
from the bimb connecting the CoII ions, with the Co···Co
distances are 12.861 and 12.745 Å, respectively (Fig. 6). Then
those chains hinged together, further given a 3D frameworks
(Fig. 7). At the sight of topology, the final structure of 2 can be
defined as a 5-connected bnn net with the Schläfli symbol of
(46·64) by denoting the [Co2(COO)2]n SBUs to 5–connected
nodes, and all the organic ligands as linkers, respectively (Fig.
S4 and Fig. 8).
O atoms from three different OIP2- ligands [Co(2)–O(2) =
2.0401(19) Å, Co(2)–O(3)D = 2.065(2) Å, and Co(2)–O(8)D =
2.017(2) Å], two N atoms from two bimb ligands [Co(2)–N(2)
= 2.092(3) Å, and Co(2)–N(4) = 2.127(3) Å], respectively.
3.1.3. [Zn(OIP)(bimb)]n (3)
The single-crystal X-ray diffraction analysis reveals that
compound 3 crystallizes in the monoclinic system, P21/n space
group, and the asymmetric unit of 3 consists of one ZnII ions,
one OIP2- ligand, and one bimb ligand. As shown in Fig. 9,
each ZnII ion is surrounded by two O atoms [Zn(1)–O(1) =
1.9728(15) Å and Zn(1)–O(3)D = 1.9750(16) Å] from two
individual OIP2- ligands and two N atoms [Zn(1)–N(1) =
2.031(2) Å and Zn(1)–N(3) = 2.0178(19) Å] from bimb ligands,
showing a tetrahedral geometry. And the angles around the ZnII
ions fall in the range of 94.32(7)−120.36(8)º, respectively.
Similar with that in complex 1, a 1D flat [Zn(OIP)]n chain
was constructed from the OIP2- ligands linked with ZnII ions
through the monodentate carboxyl groups (Fig. S5). And the
OIP2- ligand separated Zn···Zn distance is 9.615 Å. Moreover,
the bridging bimb ligands coordinated with the ZnII ions,
forming a 1D wave [Zn(bimb)]n chain (Fig. S6). And then the
two kinds of chains joined together by sharing the metal centres,
finally given a 2D bilayer (Fig. 10). The adjacent sheets were
further expanded to a 3D supramolecular structure through the
conjugation effect (Fig. 11). In the view of topology, the 3D
supramolecular framework can be simplified the 6-connected
pcu net with (412.63) topological symbol (Fig. 12).
Figure 5. The asymmetric unit of complex 2 (Symmetry codes: A: 1−x,
−y, 2−z; B: 1/2+x, 1/2−y, −1/2+z; D: −x+1, y, z).
Figure 6. The unprecedented 1D right- and left-handed [Co(bimb)]n
helix chains.
Figure 7. The 3D frameworks of complex 2.
Figure 9. The asymmetric unit of complex 3 (Symmetry codes: B:
3/2−x, −1/2+y, −1/2−z; D: −1/2+x, 1/2−y, 1/2+z).
Figure 8. The tiling featured bnn net for complex 2.
The OIP2- ligands link CoII ions to form a 1D [Co(OIP)]n
ladder chains with the binuclear [Co2(COO)2]n SBUs (Fig. S3).
6

handed helix characteristics in 2. For complex 3, the ZnII
ion has a preference to locate in a tetrahedral geometry, and
hence the ZnII ions linked by OIP2- ligands to form a 1D flat
[Zn(OIP)]n chain. The bimb ligands connected with ZnII
ions, formed a 1D [Zn(bimb)]n wave chain. Then the 1D
[Zn(OIP)]n chains and [Zn(bimb)]n wave chains further
expanded the structures to a 2D wave sheet. The comparison
study reveals that the metal ions play important roles in
determining the structural diversity of coordination
polymers. And the mixed ligands strategy expanded the
field of functional coordination polymers.
3.3. Powder X-ray diffraction (PXRD) and IR Spectra
Figure 10. The 2D wave [Zn(OIP)(bimb)] sheet containing the 1D
[Zn(bimb)]n and 1D [Zn(OIP)]n chains.
In order to check the phase purity of these complexes, the
PXRD patterns of title complexes were checked at room
temperature. As shown in Fig. S7, the peak positions of the
simulated and experimental PXRD patterns are in agreement
with each other, demonstrating the good phase purity of the
complexes. The dissimilarities in intensity may be due to the
preferred orientation of the crystalline powder samples.
The main features of IR spectra for complexes 1, 2 and 3
concerned the carboxyl groups of H2OIP ligand. As can be seen
in Fig. S8, no strong absorption peaks around 1800 cm-1 for –
COOH are observed, which implies that carboxyl groups of
organic moieties in the title complexes are completely
deprotonated. The strong peaks at 1569 and 1421 cm-1 for 1,
1623 and 1461 cm-1 for 2, and 1693, and 1486 cm-1 for 3 may
be attributed to the asymmetric and symmetric vibrations of
carboxyl groups. The (νas-νs) values (148 cm-1 for 1, 164 cm-1
for 2, and 207 cm-1 for 3) are attributed to the diverse
carboxylate coordination modes, which are in accordance with
the spectroscopic criteria on determining the modes of the
carboxylate binding (△(chelating) < △(bridging) < △(ionic) <
△(monodentate)) [34].
Figure 11. The 3D packing supramolecular structures of complex 3.
3.4.Thermal analysis
The experiments were performed on samples consisting of
numerous single crystals under N2 atmosphere with a heating
rate of 10 °C min-1, as shown in Fig. S8. For complex 1, a
weight loss of 3.8 % was observed around 100 °C, which
corresponds to the loss of the lattice water molecules (calcd 3.6
%), and then the network began to decompose with the loss of
two organic ligands at about 335 °C, with the residual weight
is ca. 16.2 % (Calcd. for CuO: 15.9 %). Similar with complex 1,
complex 2 shows a weight loss of 1.91 % in the temperature
range of 90-120°C corresponding to the release of the free
water molecules (calcd 1.86 %) and the decomposition of the
residue occurred at 360°C. The residual weight is ca. 19.6 %
(Calcd. for CoO: 18.7 %). For complex 3, the network can be
exist stably until the temperature up to 280 °C, and then the
subsequent significant weight losses occur after the onset
temperature with the residual weight is ca. 17.3 % (Calcd. for
ZnO: 16.7 %). It is obvious that the thermal stability of 2 is
higher than that of 1 and 3.
Figure 12. The hydrogen bonds based pcu net for the 3D
supramolecular structure of complex 3.
3.2. Coordination preferences and structure diversity
Complexes 1-3 were synthesized under similar reaction
condition except the use of different transition metal ions
(CuII, CoII, and ZnII), their coordination structures with
different dimensionalities and diversity architectures can be
mainly ascribed to the different coordination preferences of
metal ions. Indeed, CuII ions trend to be cheated by two
cheating carboxyl groups from OIP2- ligands, forming a 1D
flat [Cu(OIP)]n chain. And each bimb bridged two
neighbouring CuII ions, constructed
a
1D straight
[Cu(bimb)]n chain. The two kinds of chains joined together,
finally given a 2D sql sheet. For complex 2, the CoII ions
tend to form dinuclear units by two µ2-η1,η1-bridging
carboxyl groups, and the dinuclear units are further
interlinked by OIP2- ligands to form a 1D ladder chain.
Besides, the bimb linked the CoII ions, giving an
unprecedented [Co(bimb)]n chain with right- and left-
7

Inorganic Chimica Acta Volume (2015) Page
4. Conclusions
In summary, three multi-dimensional MOFs were isolated
from the hydrothermal reactions by the employment of 5-
hydroxy isophthalic acid (H2OIP) and 1,3-bis(1H-imidazol-4-
yl)benzene) (bimb). Complexes 1–3 displayed appealing
structural features from 2D layers to 3D frameworks. Structural
analyses reveals that H2OIP is an effective ligand with rich
coordination modes, which is useful to better understand the
synthon selectivity in multifunctional crystal structures. In
addition, the employment of the bimb bridging ligands during
the assembly of the metal–polycarboxylate system often leads
to structural changes and affords new frameworks.
Acknowledgements
Figure 13. The temperature dependence of magnetic susceptibility of 2
under a static field of 1000 Oe.
The work was supported by financial support from the
Natural Science Foundation of China (Grant Nos. 21101097,
21451001), key discipline and innovation team of Qilu
Normal University.
3.5. Magnetic property of complex 2.
As shown in Fig. 13, the χMT values for 2 at room
temperature are 3.39 cm3 K mol-1 (Fig. 13), which is smaller
than that for two isolated CoII cations (3.75 cm3 K mol-1),
which can be attributed to the contribution to the susceptibility
from orbital angular momentum at higher temperatures. With
the temperature decreasing, the χMT value decreases
continuously to 0.47 cm3 K mol-1 at 2 K. And the temperature
dependence χM followed the Curie-Weiss law χM= C/(T–θ)
with C= 3.96 cm3 K mol-1, θ= –39.68 K. The negative value of
θ indicates the presence of an antiferromagnetic interaction
between the nearest CoII ions. The fitting result is comparable
with those reported CoII dinuclear coordination polymers [35].
Appendix A. Supporting information
Supplementary data associated with this article can be found
in
the
online
version
at
http://dx.doi.org/10.1016/j.ica.2015.xx.xxx.
References
[1] A. Proust, B. Matt, R. Villanneau, G. Guillemot, P. Gouzerh, G.
Izzet, Chem. Soc. Rev. 41 (2012) 7605.
[2] H.C. Zhou, J.R. Long, O.M. Yaghi, Chem. Rev. 112 (2012) 673.
[3] X.T. Zhang, D. Sun, B. Li, L.M. Fan, B. Li, P.H. Wei, Cryst.
Growth Des. 12 (2012) 3845.
[4] C.J. Sumby, Coord. Chem. Rev. 255 (2011) 1937.
[5] D.S. Li, Y.P. Wu, J. Zhao, J. Zhang, J.Y. Lu, Coord. Chem. Rev.
261 (2014) 1.
[6] L.M. Fan, X.T. Zhang, D.C. Li, D. Sun, W. Zhang, J.M. Dou, Cryst.
Eng. Comm. 15 (2013) 349.
[7] F.T. Xie, H.Y. Bie, L.M. Duan, G.H. Li, X. Zhang, J.Q. Xu, J. Solid
State Chem. 178 (2005), 2858.
[8] L.L. Liu, C.X. Yu, Y.R. Li, J.J. Han, F.J. Ma, L.F. Ma, Cryst. Eng.
Comm. 17 (2015) 653.
[9] X.T. Zhang, L.M. Fan, Z. Sun, W. Zhang, D.C. Li, J.M. Dou, L.
Han, Cryst. Growth Des. 13 (2013) 792.
[10] M. Du, X.J. Zhao,J.H. Guo, S.R. Batten, Chem. Commun. (2005)
4836.
[11] F. Guo, F. Wang, H. Yang, X.L. Zhang, J. Zhang, Inorg. Chem. 51
3.6. Photoluminescent property of complex 3
The photoluminescence spectra of the two organic ligands
and complex 3 were examined in the solid state at room
temperature and given in Fig. 14. Intense emission band of pure
free H2OIP and bimb ligands have been observed at 380 nm
(λex = 280 nm), and 338 nm (λex = 290 nm), respectively, which
can be presumed that the peak originate from the π*→n or
π*→π transitions [36, 37]. It can be observed that intense
emissions occur at 358 nm (λex = 323 nm) for 3. The emission
peak of complex 3 is red shift by about 20 nm compared to the
bimb ligand, but it is also blue shift by about 22 nm compared
to the free H2OIP ligand, respectively. The emissions of
complex 3 is tentatively assigned to the intraligand transition
due to their similarity to ligands, since ZnII ion is difficult to
oxidize or to reduce due to its d10 configuration [38].
(2012) 9677.
[12] X. Zhang, L. Fan, W. Fan, B. Li, X. Zhao, Cryst. Eng. Comm. 17
(2015) 6681
[13] J. Jin, D. Li, L. Li, X. Han, S. Cong, Y. Chi, S. Niu, Inorg. Chim.
Acta 379 (2011), 44.
[14] L.L. Liu, C.X. Yu, F.J. Ma, Y.R. Li, J.J. Han, L. Lin, J.F. Ma,
Dalton Trans. 44 (2015) 1636.
[15] F. Guo, Inorg. Chim. Acta 399 (2013), 79.
[16] Y. Xu, D. Yuan, B. Wu, L. Han, M. Wu, F. Jiang and M. Hong,
Cryst. Growth Des. 6 (2006) 1168.
[17] X.T. Zhang, L.M. Fan, X. Zhao, D. Sun, D.C. Li, J.M. Dou, Cryst.
Eng. Comm. 14 (2012) 2053.
[18] Y.X. Sun, W,Y. Sun, Cryst. Eng. Comm. 17 (2015) 4045.
[19] J. Bai, H.-L Zhou, P.-Q. Liao, W.-X. Zhang, X.-M. Chen, Cryst.
Eng. Comm. 17 (2015) 4462.
[20] L. Fan, X. Zhang, W. Zhang, Y. Ding, W. Fan, L. Sun, X. Zhao,
Cryst. Eng. Comm. 16 (2014) 2144.
[21] G. Xu, F. Guo, Inorg. Chem. Commun. 27 (2013) 146.
Figure 14. Emission spectra of two organic ligands and complex 3 in
the solid state at room temperature.
[22] X. Zhang, L. Fan, W. Zhang, W. Fan, L. Sun, X. Zhao,
8

Cryst. Eng. Comm. 16 (2014) 3203.
(2015) 39854.
[31] G.M. Sheldrick, SHELXS-97, Program for solution of crystal
structures, University of Göottingen, Germany, 1997.
[32] G. M. Sheldrick, SHELXL-97, Program for refinement of crystal
structures, University of Göottingen, Germany, 1997.
[33] V.A. Blatov, M. O'Keeffe, D.M. Proserpio, Cryst. Eng. Comm. 12
(2010) 44.
[34] L.M. Fan, X.T. Zhang, Z. Sun, W. Zhang, Y.S. Ding, W.L. Fan,
L.M. Sun, X. Zhao, H. Lei, Cryst. Growth Des. 13 (2013) 2462.
[35] M.L. Han, Y.P. Duan, D.S. Li, H.B. Wang, J.Zhao, Y.Y. Wang,
Dalton Trans. 43 (2014) 15450
[36] K. Jiang, L.-F. Ma, X.-Y. Sun, L.-Y. Wang, Cryst. Eng. Comm. 13
(2011) 330.
[37] B.-F. Huang, T. Sun, Z. Sharifzadeh, M.-Y. Lv, H.-P. Xiao, X. -H.
Li, A. Morsali, Inorg. Chim. Acta 405 (2013) 83.
[38] T. Cao, Y. Peng, T. Liu, S. Wang, J. Dou, Y. Li, C. Zhou, D. Li, J.
Bai, Cryst. Eng. Comm. 16 (2014) 10658.
[23] L. Fan, X. Zhang, W. Zhang, Y. Ding, W. Fan, L. Sun, Y.
Pang, X. Zhao, Dalton Trans. 43 (2014) 6701
[24] L. Fan, W. Fan, W. Song, L. Sun, X. Zhao, X. Zhang,
Dalton Trans. 43 (2014) 15979.
[25] L. Fan, Y. Gao, G. Liu, W. Fan, W. Song, L .Sun, X. Zhao,
X. Zhang, Cryst. Eng. Comm. 16 (2014) 7649.
[26] L. Fan, W. Fan, B. Li, X. Liu, X. Zhao, X. Zhang, Dalton
Trans. 44 (2015) 2380
[27] M. Dai, X.-R. Su, X. Wang, B. Wu, Z.-G. Ren, X. Zhou
,J.-P. Lang, Cryst. Growth Des. 14 (2014) 240.
[28] Z.-H. Yan, L.-L. Han, Y.-Q. Zhao,X.-Y. Li, X.-P. Wang,
L., D. Sun, Cryst. Eng. Comm. 16 (2014) 8747.
[29] J.-J. Wang, L. Tang, M.-L. Zhang, L.-J. Gao, Y.-X. Ren, X.-Y.
Hou, F. Fu, J. Mol. Struct. 1085 (2015) 215.
[30] L. Fan, W. Fan, B. Li, X. Zhao, X. Zhang, RSC Adv. 5
9