A Ni(II) ferromagnet with mixed pyridine-3,5-dicarboxylate-1,4-bis(imidazol-l-yl)butane heterobridges exhibiting long-range ordering and hysteresis loop

Article abstract of DOI:10.1016/j.inoche.2016.04.023

A rare Ni-ferromagnet [Ni(pdc)(bib)]·2H₂O (H₂pdc = pyridine-3,5-dicarboxylic acid, bib = 1,4-bis (imidazol-l-yl)butane) has been prepared, which possesses a 3D supramolecular network based on (3,5)-connected helical-armed 2D layers. Interestingly, at high temperature (> 12.7 K), 1 exhibits a weak ferromagnetism, whereas at low temperature, it shows unusual long-range ordering (LRO) behaviors combining spin canting and hysteresis loop.

Full text of DOI:10.1016/j.inoche.2016.04.023

Inorganic Chemistry Communications 69 (2016) 31–34
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Short communication
A Ni(II) ferromagnet with mixed
pyridine-3,5-dicarboxylate-1,4-bis(imidazol-l-yl)butane heterobridges
exhibiting long-range ordering and hysteresis loop
a,b
a
a
a
a,
b,
Min-Le Han , Xue-Qian Wu , Guo-Wang Xu , Guo-Xuan Wen , Dong-Sheng Li ⁎, Lu-Fang Ma ⁎
a
College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy
Conversion Materials, China Three Gorges University, Yichang 443002, PR China
b
College of Chemistry and Chemical Engineering, Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471022, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A rare Ni-ferromagnet [Ni(pdc)(bib)]·2H O (H pdc = pyridine-3,5-dicarboxylic acid, bib = 1,4-bis (imidazol-l-yl)
2
2
Received 20 March 2016
Received in revised form 17 April 2016
Accepted 21 April 2016
butane) has been prepared, which possesses a 3D supramolecular network based on (3,5)-connected helical-
armed 2D layers. Interestingly, at high temperature (N12.7 K), 1 exhibits a weak ferromagnetism, whereas at
low temperature, it shows unusual long-range ordering (LRO) behaviors combining spin canting and hysteresis
loop.
Available online 22 April 2016
Crown Copyright © 2016 Published by Elsevier B.V. All rights reserved.
Keywords:
Ni -CPs
II
Pyridine-3,5-dicarboxylic acid
1,4-bis(imidazol-l-yl)butane
Magnetic property
Coordination polymers (CPs) based on parmagnetic metal ions
exhibiting extended structures are of intense current interest in the
field of molecular magnetism and materials chemistry due to their
various structural topologies and potential applications as functional
materials [1–5]. These materials have also offered great opportunities
to better understand fundamental magnetic phenomena, such as long-
range ordering (LRO), spin canting, metamagnetism, anisotropy, relax-
ation dynamics, and so on [6]. As far as LRO is concerned, some complex
and exotic behaviors have been revealed in molecular systems, for
example, the combination of magnetic properties and other functions
by the carboxylate group can transmit the magnetic coupling in differ-
ent degrees, and the coordination of the pyridyl and carboxylate groups
in these ligands may result in extended frameworks [10–14].
Meanwhile, the design, syntheses and applications of metal-organic
hybrid materials based on mixed-ligands (multicarboxylate and flexible
N-donor ligands) also have so far attracted unparalleled attention in
research [15–17]. The flexibility of N-donor ligands can adopt different
conformations and thus lead to distinct symmetries during the self-
assembly process [18]. As part of our investigations on the structural
diversity, magnetism properties of metal-organic hybrid materials
[7]. The key factors in the design and synthesis of these CPs with desir-
2
based on mixed-ligands, herein, pyridine-3,5-dicarboxylic acid (H pdc)
able properties and expected structures are mainly focused on the
appropriate selection of nodes (metal ions or metal-including clusters)
and spacers (organic ligands) [8]. When organic ligands coupled with
a parmagnetic metal ion, these ligands may cite peculiar magnetic
behaviors e.g. (anti)ferromagnetism, magnetoelectricity and multi-
ferroicity [9]. Among organic ligands, multidentate ligands containing
carboxylate and a pyridyl group, such as nicotinate, isonicotinate, and
pyridine-dicarboxylate, have been frequently used in the preparation
of magnetic materials, because the various coordination modes adopted
and 1,4-bis(imidazol-l-yl)butane (bib) were selected as a bridging ligand
and reacted with Ni(II) ions, giving rise to a new metal-organic hybrid
materials, namely [Ni(pdc)(bib)]·2H
properties were also investigated and discussed in detail.
Reaction of H pdc with bib and Ni(II) acetate at 140 °C for 3 days
2
O (1). Moreover, their magnetic
2
under hydrothermal conditions generates green crystalline product 1
[19]. The compositions were confirmed by elemental analysis and IR
spectra, and powder X-ray diffraction. Single crystal X-ray diffraction
study [20] reveals that complex 1 crystallizes in a monoclinic system
1
with space group P2 /n and has a 3-D supramolecular framework
work based on 2-D layers. All Ni sites are six-coordinated with a
distorted octahedron geometry by three carboxylate-oxygen atoms
⁎
Corresponding authors at: College of Materials and Chemical Engineering, China Three
O1, O2 and O3#1, symmetry code: #1, −x + 1, y, z) from two pdc2
−
,
(
Gorges University, Yichang 443002, PR China.
E-mail addresses: lidongsheng1@126.com (D.-S. Li), mazhuxp@126.com (L.-F. Ma).
one nitrogen atom (N1#2, symmetry code: #2, −x + 1/2, y + 1/2,
http://dx.doi.org/10.1016/j.inoche.2016.04.023
1387-7003/Crown Copyright © 2016 Published by Elsevier B.V. All rights reserved.

32
M.-L. Han et al. / Inorganic Chemistry Communications 69 (2016) 31–34
−
z + 1/2.) from pdc2−, and two trans-nitrogen atoms (N2 and N5#2)
from two bib ligands with the angle of N2-Ni1-N5#2 of 175.7° (Fig. S1,
Supporting Information). The pdc2 ligand adopts a (κ -κ )-(κ )-(κ )-
-bridge linking three Ni(II) ions to form a 2D layer, moreover, the
bib ligand with TGG conformation (T = trans, G = gauche) bridge
Ni(II) ions to generate a 2 helical chain along [010] axis with the
−
1
1
1
1
μ
3
1
pitch of 12.5 Å, which decorate the 2D layer at two sides in an outward
fashion, resulting in a interesting helical-armed 2D network. Analysis
of the network topology of 1 reveals that each Ni(II) center acts as a
2
−
5
-connected node to connect three pdc ligands and two bib spacers.
2
−
And the pdc ligands serve as the 3-connected nodes. Thus, a (3,5)-
connected network with the point symbol of (3·5 )(3 ·5 ·6 ·7) is
constituted (Fig. S2, Supporting Information ). There are evident inter-
2
2
3
4
†
molecular π⋯π stacking interactions between the adjacent imidazol
ring of the adjacent 2D layers with co-facial distances of 3.66 and
3
.78 Å (Fig. 1), which extend these 2D with ABAB stacking fashions to
−1
M M
Fig. 2. Temperature dependence of χ T and χ for 1. Open points are the experimental
build final 3-D supramolecular framework (Fig. 1).
data, and the solid line represents the best fit obtained from the Curie-Weiss law.
Phase purities of the bulky materials of 1 were confirmed by powder
†
X-ray diffraction (PXRD) patterns (see Fig. S3, SI ). The experimental
and simulated PXRD patterns agree well with each other, confirming
interactions between the adjacent Ni(II) ions. Upon further cooling to
the good phase purity. Additionally, the thermogravimetric analysis of
M M
2 K, χ T decreases quickly. The steep declines in χ T at low tempera-
1
was carried out under an air atmosphere (Fig. S4, Supporting
ture clearly indicate that a kind of spontaneous magnetization emerges.
This phenomenon in a ferromagnetic system could be attributed to
weak antiferromagnetism, owing to spin canting: the antiferromagnetic
coupled spins from different sublattices are not parallel, but canted
to each other, and the resulting net moments are correlated in a
antiferromagnetic-like fashion and develop into LRO below the critical
temperature.
To characterize the low-temperature behaviors of 1, FC (field-
cooled) and ZFC (zero-field-cooled) magnetization measurements
were performed under 50 Oe (Fig. 3a). The ZFC magnetization shows
†
Information ). The first weight lost of 7.8% was observed from 115 °C
to 198 °C corresponding to the lost of free water molecules (calcd.
8
final residue of 24.2% is close to the calculated 24.6% based on NiO.
The temperature-dependent magnetic susceptibilities were mea-
sured on polycrystalline samples of 1 at 1000 Oe in the range of 1.8–
.0%). Then pyrolysis of the sample occurred from 325 to 490 °C. The
−
1
3
00 K in Fig. 2. For 1, the value of χ
which is larger than the spin-only value (1.0 cm mol
for a magnetically isolated Ni(II) ion. The χ T value increases gradually
upon cooling to ca. 35 K. Below this temperature, χ T value increases
abruptly to a maximum of 4.69 cm3 mol ·K at 12.7 K. Above 15 K,
the temperature dependence of 1/χ obeys the Curie-Weiss law with
M
T at 300 K is 1.54 cm mol
K,
−
1
K) expected
M
M
−1
M
−
1
C = 1.49 cm K mol and θ = 4.91 K, revealing dominant ferromagnetic
Fig. 3. (a) Low temperature dependence of the magnetic susceptibility (χ) for 1 measured
under zero field cooling (ZFC) and field cooling (FC) conditions. (b) Field-dependent
magnetization for 1 measured at 2.0 K. Insert: M versus H hysteresis loops for 1.
Fig. 1. (a) 2D layer in 1. (b) 3D supramolecular structure of 1 and R- and L-handed helical
chains.

M.-L. Han et al. / Inorganic Chemistry Communications 69 (2016) 31–34
33
a peak at 12 K and diverges from the FC magnetization at about 13 K.
This kind of divergence further confirms a LRO of ferromagnetic
components. These data can be found in the supporting file. Supple-
mentary data to this article can be found online at http://dx.doi.org/
10.1016/j.inoche.2016.04.023.
interactions. In addition, the critical temperature (T
by the positions of the negative peak on the derivative dM/dT (M =
magnetization) of FC data [7e], is 14.2 K. The T value is confirmed by
c
), determined
c
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2
O (1). A mixture of H
2
pdc (0.10 mmol, 16.1 mg),
bib (0.10 mmol, 19.0 mg), Ni(OAc)
2
·4H O (0.10 mmol, 24.9 mg), and H
2
2
O (8 mL)
was placed in a 25 mL Teflon-lined stainless steel vessel, heated to 140 °C for
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5 6
−1
N, 15.51. IR (KBr, cm ): 3450 w, 1637 s, 1580 m, 1522 m, 1390 s, 780 m, 762 s,
665 m.
(
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(
(
displaying reversibly shrinking and expanding pore modulation, CrystEngComm
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5 6
H21NiN O (Mr = 450.10),
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