Spin canting and long-range magnetic ordering in a 2-D cobalt-organic framework incorporated with a new bent connector: 1,4-bis(5-(4-pyridyl)-1H-1,2, 4-triazol-3-yl)benzene

Article abstract of DOI:10.1016/j.inoche.2013.02.012

A 2-D cobalt-organic framework formulated as [Co(bdc)(bptb)]_n (1), built from a mixed 1,2-benzenedicarboxylate anion (bdc), 1,4-bis(5-(4-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (bptb), and cobalt salt, has been hydrothermally synthesized and characterized. Complex 1 has a [Co(bdc)]_n chain structure in which the chains are isolated by the bptb ligands in a 2-D wave-like architecture. The magnetic behavior of complex 1 was studied, and it indicated the coexistence of spin-canted weak ferromagnetism with T_N = 10 K and long-range magnetic ordering.

Full text of DOI:10.1016/j.inoche.2013.02.012

Inorganic Chemistry Communications 31 (2013) 18–22
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Spin canting and long-range magnetic ordering in a 2-D cobalt–organic
framework incorporated with a new bent connector:
1,4-bis(5-(4-pyridyl)-1H-1,2,4-triazol-3-yl)benzene
Fu-Ping Huang a,b, Peng-Fei Yao a, Qing Yu a, Di Yao a, He-Dong Bian a,
,
⁎
Hai-Ye Li a, Jin-Lei Tian b, Shi-Ping Yan b,
⁎
a
Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, Department Chemistry and Chemical Engineering, Guangxi Normal University, Ministry of Education of China,
Guilin 541004, PR China
b
Department of Chemistry, Nankai University, Tianjin 300071, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A 2-D cobalt–organic framework formulated as [Co(bdc)(bptb)]n (1), built from a mixed 1,2-benzenedicarboxylate
anion (bdc), 1,4-bis(5-(4-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (bptb), and cobalt salt, has been hydrothermally
synthesized and characterized. Complex 1 has a [Co(bdc)]n chain structure in which the chains are isolated by the
bptb ligands in a 2-D wave-like architecture. The magnetic behavior of complex 1 was studied, and it indicated
the coexistence of spin-canted weak ferromagnetism with TN=10 K and long-range magnetic ordering.
© 2013 Elsevier B.V. All rights reserved.
Received 27 November 2012
Accepted 7 February 2013
Available online 15 February 2013
Keywords:
Crystal structures
Bent ligand
Spin canting
Introduction. To better understand some fundamental magnetic
phenomena such as: ferromagnetic, ferrimagnetic, antiferromagnetic,
and so on, magnetic coordination polymers provide good examples
in molecular magnetism [1]. The ferrimagnetic correlations can be
attributed to spin canting, i.e., perfect antiparallel alignment of the
spins on the neighboring metal ions is not achieved, so that residual
spins are generated [2]. It is well known that spin canting can arise
from two contributions: (1) the presence of an antisymmetric ex-
change and (2) the existence of single-ion magnetic anisotropy.
Beyond that, the mutually tilted orientation of the metal centers
caused by bent spacers, could give further contribution to the canting
effect [3].
In the recent years, various coordination polymers with interest-
ing magnetic properties had been synthesized based on the rigid an-
gular ligands [3,4]. Our group had reported a series of CoII/NiII
coordination polymers, based on three angular N-heterocyclic-like li-
gands: 1H-3,5-bis(4-pyridyl)-1,2,4-triazole (4,4′-bpt), 1H-3-(3-pyridyl)-
5-(4-pyridyl)-1,2,4 -triazole (3,4′-bpt), 1H-3,5-bis(3-pyridyl)-1,2,4-
triazole (3,3′-bpt) (Chart 1). Most of them have fascinating structures
and interesting magnetic properties [5].
which has a bent backbone: the angle subtended at the center of the
benzene ring and two pyridyl N-donors is 174° (Scheme 1). Based
on bptb, we have synthesized a new complex [Co(bdc)(bptb)]n
(1), which possesses a 2-D wave-like architecture and shows the
coexistence of spin canting and magnetic long-range ordering (LRO).
Experimental section: Materials and physical measurements. With
the exception of the ligands of bptb which were prepared according to
the literature procedure [6], all reagents and solvents for synthesis
and analysis were commercially available and used as received. IR
spectra were taken on a Perkin-Elmer Spectrum One FT-IR Spectrometer
in the 4000–400 cm−1 region with KBr pellets. X-ray powder diffraction
(XRPD) intensities were measured on a Rigaku D/max-IIIA diffractome-
ter (Mo-Ka λ=0.71073 Å). Elemental analyses for C, H, and N were
carried out on a Perkin-Elmer model 2400 II elemental analyzer.
Temperature- and field-dependent magnetic measurements were car-
ried out on a SQUID-MPMS-XL-7 magnetometer. Diamagnetic correc-
tions were made with Pascal's constants.
Preparation of 1. A mixture containing Co(NO3)2·6H2O (145 mg,
0.5 mmol), bptb (183 mg, 0.5 mmol), H2(bdc) (83 mg, 0.5 mmol),
NaOH (40 mg, 1 mmol), water (10 mL) and ethanol (5 mL) was
sealed in a Teflon-lined stainless steel vessel (25 mL), which was
heated at 140 °C for 3 days and then cooled to room temperature at
a rate of 5 °C/h. Red block crystals of 1 were obtained and picked
out, washed with distilled water and dried in air. Yield: 47% (based
on Co(II)). Elemental analysis for C28H18CoN8O4 (%) Calcd: C, 57.05;
H, 3.06; N, 19.02. Found: C, 57.17; H, 3.15; N, 19.14. IR (KBr, cm−1):
3215w, 1605 m, 1584 s, 1558 m, 1393 s, 852 m, 754 m, 718 s, 691 m.
As an extension of this work, we introduce herein a new bridging
ligand: 1,4-bis(5-(4-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (bptb),
⁎
Corresponding authors.
E-mail addresses: gxnuchem312@yahoo.com.cn (H.-D. Bian), yansp@nankai.edu.cn
(S.-P. Yan).
1387-7003/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.inoche.2013.02.012

F.-P. Huang et al. / Inorganic Chemistry Communications 31 (2013) 18–22
19
Chart 1. The three positional isomeric bent ligands used before.
174°
molecules, and two bdc anions. Each Co(II) ion lies in a distorted octahe-
dral coordination environment, which is equatorially coordinated by
four carboxylic O atoms from two bdc anions [Co1–O falls into the
range from 2.069 (4) Å to 2.186 (4) Å], and axially occupied by two N
atoms from two bptb ligands [Co1–N1=2.177 (4) Å; Co1–N8C=2.168
(5) Å symmetry codes: C x−1, y+1, z−1].
HN
N
Adjacent Co(II) centers are linked by the carboxylic groups of bdc
anion via bis(μ-oxo) and bis(μ-O,O′-carboxylato) bridges alternately
to form infinite [Co(bdc)]n chains running along the crystallographic
a axis (Fig. 3). The distance of the adjacent Co(II) centers linked by
the carboxylic groups of bdc anion via bis(μ-oxo) bridges is 3.328(8)
Å. And the distance of the adjacent Co(II) centers linked by the
carboxylic groups of bdc anion via bis(μ-O,O′-carboxylato) bridges
league is 4.42(1) Å.
N
N
N
N
N
NH
Scheme 1. The possible coordination configuration of bptb.
X-ray structure determination. X-ray single-crystal diffraction data
The neighboring [Co(bdc)]n chains are also bridged by bent bptb li-
gand to generate a wave-like layer structure (Fig. 4) with the Co…Co
distance of 21.76(5) Å. In addition, the N3 of bptb as the H-donor link
the uncoordinated carboxylate O (O2) of a neighboring layer through
hydrogen bonding interactions to furnish a 3-D architecture (Fig. S1 in
the Supporting information).
for bptb and 1 were collected with a Bruker SMART CCD instrument
respectively by using graphite monochromatic Mo-Kα radiation
(λ=0.71073 Å). The data were collected at 293(2) K and there was
no evidence of crystal decay during data collection. A semiempirical
absorption correction was applied using SADABS, and the program
SAINT was used for integration of the diffraction profiles. The struc-
ture was solved by direct methods with the program SHELXS-97
and refined by full-matrix least-squares methods on all F2 data with
SHELXL-97 [7]. The non-hydrogen atoms were refined anisotropical-
ly. Hydrogen atoms bound to carbon and nitrogen were placed geo-
metrically and allowed to ride during the subsequent refinements
with isotropic displacement parameters. The starting positions for hy-
drogen atoms of water molecules were found in difference syntheses
and then fixed in the given positions. The final cycle of full-matrix
least-squares refinement was based on observed reflections and var-
iable parameters. Crystallographic data and structural refinement de-
tails of bptb and 1 are summarized in Table S1. Selected bond lengths
and bond angles of 1 are given in Table S2.
Results and discussion: Description of the crystal structures of
bptb·2H2O. X-ray single-crystal structural analysis reveals that
bptb·2H2O crystallizes in the monoclinic space group P21/c with an
asymmetric unit consisting of half a bptb and one water molecule
(Fig. 1a). The adjacent bptb molecules are linked together by water
molecules through O–H…N hydrogen bonds (Table S3), forming a
three-dimensional supramolecular network (Fig. 1b).
Description of the crystal structures of 1. Single-crystal X-ray struc-
tural analysis shows that the structure of 1 is a wave-like layer complex
(Fig. 2). The asymmetric unit of 1 consists of one Co(II) cation, two bptb
The XRPD result of 1: In order to confirm the phase purity of
the sample, X-ray powder diffraction (XRPD) experiments have
been carried out for complexes 1, before the magnetic measurements.
The XRPD experimental and computer-simulated patterns of 1 are
shown in Fig. S2. Although the experimental patterns have a few
unindexed diffraction lines and some are slightly broadened in com-
parison with those simulated from the single crystal models, it still
can be considered favorably that the samples of 1 are phase pure.
The magnetic properties of 1: Solid-state variable-temperature mag-
netic susceptibility measurements were performed on a powder sample
of complex 1 in the 2–300 K range in a 1 kOe magnetic field (Fig. 5a).
The Curie–Weiss fit of the inverse magnetic susceptibility above 70 K
provides a Curie constant C=3.80 cm3 K·mol−1 and Weiss tem-
perature θ=−34.05 K. The χM T value per Co(II) at 300 K is about
3.44 emu·K·mol−1
, much larger than the spin-only value
1.88 emu·K·mol−1 for a magnetically Co(II) ion with (S=3/2,
g=2.0), as expected for the presence of a strong orbital contribu-
tion in octahedral Co(II). From 300 to 35 K, the magnetic moments
decrease with the decreasing temperature, which basically corre-
sponds to a single-ion behavior, which accounts for the splitting of
the 4T1 term into six Kramers doublets as a consequence of the com-
bined effect of spin-orbit coupling and distortion from ideal octahedral
symmetry [1d,8]. However, the observed increase in χMT below this
a
b
O1A
N2
N3
C5
C4
C6
C10
C8
N1
C7
C3
N4
C1
C2
C9
O1
Fig. 1. The molecular structure (a) and the extended structure of the three-dimensional supramolecular network of bptb·2H2O (b).

20
F.-P. Huang et al. / Inorganic Chemistry Communications 31 (2013) 18–22
O2A
N7
N6
O1A
O3A
O1
O4A
N4
N5
N8
N8C
Co1
O3B
N1
O1B
O4B
N3
N2
O2B
Fig. 2. The local coordination environments of the Co(II) atoms.
Fig. 3. The [Co(bdc)]n chain viewed down the b axis.
temperature is no longer coming from the single-ion behavior but rather
from a canted antiferromagnetic Co(II)–Co(II) exchange interaction. The
final down–up behavior in χMT below 10 K indicate a magnetic phase
transition and some impurity [9].
The magnetic phase transition is also consistent with the presence of
the bifurcation point between the field-cooled (FC)/zero-field-cooled
(ZFC) magnetization curves below 10 K (Fig. 5b) [10]. At very low tem-
peratures, the FC/ZFC curves undergo a slight increase which could be
attributed to the presence of a paramagnetic contribution arising from
defects in the crystal structure [11]. In addition, the FC magnetizations
of 1 are quite field-dependent, in which the rise of the χM T values at
low temperature becomes less obvious at higher fields (Fig. 5b, inset).
This is an important feature of spin canting behavior [12].
and agreed with the previous magnetic studies, although detailed
information of the magnetic entropy could not be derived yet from
the current specific heat data, with the lattice contribution unknown
[13]. Therefore, we consider that complex 1 should be a hidden weak
ferromagnet due to spin canting. Furthermore, the absence of a
frequency dependence of ac susceptibility rules out the presence of
glassiness or the magnetic domain wall motion in 1. The FO transition
is further demonstrated by the field-dependent isothermal magneti-
zation M(H) performed at 2 K (Fig. 6b, inset). The sharp increase of
magnetization is observed below 5 kOe. When the external field is
further increased, the magnetization increases smoothly and reaches
2.61 Nβ at 50 kOe. The appearance of a maximum around 1.004 kOe
in the dM/dH curve measured at 2 K confirms that M vs. H curve
increase rapidly at low fields corroborates the spontaneous magneti-
zation behavior and a long-range FO phase transition of 1 [14]. The
magnetizations measured at 2 K show hysteresis loops with a small
coercive field (Hc) of ca. 50 Oe, and a remnant magnetization (Mr)
of 0.057 Nβ indicating a soft-magnetic behavior of 1. The spontaneous
The zero-field ac magnetic susceptibility measurement (Fig. 6a)
only exhibits the characteristic of an antiferromagnet. The in-phase
part χM´ reaches a maximum at TN =10.0 K, while no obvious out-
of-phase χM″ reflection was observed. This kind of phenomenon
clearly revealed the occurrence of a magnetic long-range ordering
Fig. 4. The wave-like layer structure of 1.

F.-P. Huang et al. / Inorganic Chemistry Communications 31 (2013) 18–22
21
12
5
1000Oe
50Oe
100
80
60
40
20
0
a
b
5.5
5.0
4.5
4.0
3.5
3.0
2.5
10
4
8
3
2
1
0
6
4
0
4
8
12
16
20
0
50 100 150 200 250 300
T/K
T/K
0
50
100
150
200
250
300
0
2
4
6
8
10 12 14 16 18 20 22
T/K
T/K
Fig. 5. (a) Plots of χMT vs. T for 1. Inset: the temperature dependence of 1/χM, the best fit of the curve (red) to the Curie–Weiss law; (b) the FC and ZFC of 1. Inset: the plots of χMT vs. T at
various fields. (For interpretation of the references to color in this figure legend, the reader is referred to the web of this article.)
2
3.0
4.5
a
b
2.5
2.0
1.5
1.0
0.5
0.0
χM'100Hz
χM"100Hz
χM'997Hz
χM"997Hz
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
1
0
0
10000
20000
30000
40000
50000
0.6
0.5
0.4
0.3
0.2
0.1
0.0
H/Oe
-1
0
10
20
30
40
50
H/KOe
0
2
4
6
8
10 12 14 16 18 20 22
-3000
-2000
-1000
0
1000
2000
3000
T/K
H/Oe
Fig. 6. (a) The temperature dependence of the in-phase (χ′) and the out-of-phase (χ″) ac magnetic susceptibilities for 1; (b) the hysteresis loop of 1 at 2 K. Inset: field dependence of
magnetization (up) and the dM/dH derivative curve (down).
magnetization observed is due to spin canting, with an estimated
canting angle of 1.24° (ψ=tan−1(Mr/Ms)) [15].
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i.e., perfect antiparallel alignment of the spins on the neighboring
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Conclusion. In summary, this paper describes the synthesis and crystal
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We gratefully acknowledge the National Nature Science Founda-
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