Coordinated Molecule-Modulated Magnetic Phase with Metamagnetism in Metal-Organic Frameworks

Article abstract of DOI:10.1021/acs.inorgchem.9b00889

Most well-known metal-organic frameworks (MOFs) possessing the magnetic Ni₂O₂(CO₂)₂ chains, called Ni-MOF-74, have been investigated with regard to magnetic properties at open-metal sites. We present the modulat

Full text of DOI:10.1021/acs.inorgchem.9b00889

Communication
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Coordinated Molecule-Modulated Magnetic Phase with
Metamagnetism in Metal−Organic Frameworks
Kwanghyo Son, Jin Yeong Kim, Gisela Schu
̈
tz, Sung Gu Kang,* Hoi Ri Moon,*,‡
†
‡
†
,§
,
⊥
and Hyunchul Oh*
†
Max Planck Institute for Intelligent Systems, Heisenbergstrasse 3, Stuttgart 70569, Germany
Department of Chemistry, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of Korea
School of Chemical Engineering, University of Ulsan, Ulsan 44610, Republic of Korea
‡
§
⊥
Department of Energy Engineering, Gyeongnam National University of Science and Technology, Jinju 52725, Republic of Korea
*
S Supporting Information
couplings should be coexist in interchain interactions with
intrachain interactions.
19,20
ABSTRACT: Most well-known metal−organic frame-
works (MOFs) possessing the magnetic Ni O (CO )
chains, called Ni-MOF-74, have been investigated with
regard to magnetic properties at open-metal sites. We
present the modulation of their magnetic phase and
metamagnetism via imidazole molecule coordination.
2
2
2 2
In this study, the feasibility of modulating magnetic phases
between AFM and FM orderings is therefore explored, as
suggested by the literature, by adjusting the coordination of the
20−23
metal ions, solvents, or organic ligands.
Furthermore, the
critical temperaturesNee
́
l temperature (T ) for AFM
N
ordering and Curie temperature (T ) for FM orderingand
C
the critical field (H ) for the metamagnetism transition can be
cr
olecule-based magnetic materials have recently attracted
increasing interest for use in novel applications (e.g.,
designed as the FM/AFM ratio in the system.
M
A hexagonal 1D-channel MOF possessing numerous OMSs
2
+
magnetic switchers, magnetic sensors, and multifunction
magnetic devices in molecular spintronics) because of their
ability to display ferromagnetism and other more complex
(Ni ), called Ni-MOF-74, was chosen as the low-dimensional
magnet for this study. The structure of Ni-MOF-74 exhibits
II
helical building units of FM Ni O 5-fold coordination
5
1
−5
magnetic phenomena.
In particular, these materials are
polyhedral chains with 2,5-dioxide-1,4-benzenedicarboxylate
organic linkers (denoted as Ni-MOF-74-ac). Then, three
different amounts of imidazole molecules (IMs) were
introduced into the OMSs in the channel of Ni-MOF-74,
herein referred to as Ni-MOF-74-IM, in order to observe the
gradual occupation of the unpaired electron at its OMS
(Figure 1). The Fourier transform infrared (FT-IR) spectra of
Ni-MOF-74-ac and three Ni-MOF-74-IMs indicate the
successful incorporation of IMs in the Ni-MOF-74 systems,
and powder X-ray diffraction (PXRD) patterns clearly indicate
that the framework structures of the samples were maintained
after the introduction of IMs (Figures S1 and S2). On the basis
advantageous because their magnetic properties can be
controlled by changing their spin center, the length of their
interactive organic ligands, or both. These advantages permit
the study of important magnetic features such as magnetic
dynamics and magnetic hysteresis with high spontaneous
magnetization. Various magnetic systems with designed novel
structures in single-molecule magnets (SMMs) and single-
6
−9
chain magnets (SCMs) have been reported.
Among the various types of molecular-based magnets,
metal−organic frameworks (MOFs) could represent a
potential model system because of their numerous metal
clusters within a microporous crystalline structure, their varied
functionality (via ligand and metal cluster exchange), and/or
their controllable cluster−cluster interactions through tunable
2
+
of the elemental analysis results, 10%, 38%, and 70% of all Ni
the OMS) in MOF-74-ac are gradually occupied by IM,
respectively, denoted as Ni-MOF-74-IM-10, Ni-MOF-74-IM-
(
1
0,11
3
8, and Ni-MOF-74-IM-70.
As IMs are introduced into the 1D channel, the square-
pore size and structure.
Moreover, open-metal sites
(
OMSs; unpaired electrons in the metal cluster) in MOFs
are very useful for understanding the influence of unpaired
II
pyramidal 5-fold-coordinated Ni ion with two unpaired
electrons is converted into the octahedral 6-fold-coordinated
Ni species with an IM. The UV−vis−near-IR (NIR) spectra
clearly show that the ratio of 6-fold-coordinated Ni is
electrons on magnetic metal ions, by the design of interior
II
12,13
structures in the frameworks.
For example, the antiferro-
II
and ferromagnetic (AFM and FM, respectively) coupling
effects on metal spin centers in OMSs can therefore be
elucidated via the gradual occupation of unpaired electrons at
increased when the amount of IM introduced is increased
2
0
(
Figure S3). This conversion ratio (from 5-fold to 6-fold at
II
1
4−18
the Ni site) results in a dramatic change in the magnetic
characteristics. Through this phenomenon, the magnetic
properties of MOFs can be investigated as a function of their
OMSs.
Moreover, the spin canting and metamagnetism
are particular types of AFM coupling effects in some low-
dimensional [layers, two-dimensional (2D); chains, one-
dimensional (1D)] systems. Because the metamagnetism
disrupts the AFM ordering and turns into the FM state
when a certain external field is applied, FM and canted AFM
Received: March 27, 2019
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b00889
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
expected spin-only value of 3.00 cm K mol for three NiII
3
−1
ions (S = 1; g = 2) because of the orbital contribution from the
II
octahedral Ni ions. The value of χ T(T) is increased slowly
m
until 25 K and then rapidly decreased to below 20 K, reaching
3
−1
∼
0.3 cm K mol for Ni-MOF-74-ac, Ni-MOF-74-IM-10, and
3
−1
Ni-MOF-74-IM-38, and 1.06 cm K mol for MOF-74-IM-70.
The linear fitting of the inverse magnetic susceptibility, 1/χm,
versus T from 150 to 300 K (linear part) to the Curie−Weiss
law [χ (T) = C/(T + θ)], where C is the Curie constant and θ
m
is the Weiss constant, indicates the existence of AFM
3
−1
configurations with C = 4.36, 3.89, and 3.48 cm mol
K
(
Figure S5). Weiss temperatures of θ = 4.96, 4.11, and 3.28 K
can be obtained for Ni-MOF-74-ac, Ni-MOF-74-IM-10, and
Ni-MOF-74-IM-38, respectively. Ni-MOF-74-IM-70, however,
exhibits FM ordering at C = 3.69 cm mol K, θ = −8.92, and
a Curie temperature, T , of 8.83 K. The χ (T) data show
3
−1
C
m
cusps at Nee
7 K for MOF-74-IM-10, and 15 K for MOF-74-IM-38; T is
́
l temperatures (T ) of ∼18.5 K for MOF-74-ac,
N
1
N
obtained at the x-axis intersection of dχ /dT to improve
m
accuracy (Figure S6). Note that Ni-MOF-74-IM-70 does not
have a cross section. The abrupt decreases below TN occur
because of interchain AFM interactions.
The combination of the Meyer model for AFM coupling (J1
<
0) and the Monford model for FM coupling (J > 0) was
2
24,25
used as a fitting model (H = −J∑S ·S )
(Figure S7). The
Figure 1. Crystal structures of Ni-MOF-74-ac, Ni-MOF-74-IM-10,
Ni-MOF-74-IM-38, and Ni-MOF-74-IM-70. (top) Primary assem-
bling unit.
i
i+1
fitting equation (1) is
l
2
2
o(g μ )
o
2 + 0.0194x + 0.777x
o
1
B
1
1
χ = Nm
m
o
2
3
temperatures and applied fields. In addition, magnetic phase
transition diagrams can also be obtained via M−T and M−H
curves.
o k T 3 + 4.346x + 3.232x + 5.834x1
o
n
B
1
1
Ä
É
Å
2 Ñ
Å
Ñ
Å (g μ ) Ñ
Å 2
B
Ñ
Å
2
Ñ
+
Å
Ñ
The direct-current (dc) magnetic susceptibilities (χ ) of the
Å
Ñ
m
Å
Ñ
Å 3 k T Ñ
Å
ÇÅ
B
Ñ
ÖÑ
samples were collected under an applied field of 1 kOe in the
range of 2−300 K. The χ T versus T and χ versus T (inset)
|
m
m
2
3 o
1
− 0.3127x + 0.124x + 0.541x o
2
2
2 o
curves of the samples are shown in Figure 2. The values of χ T
m
}
3
−1
II
2
o
o
o
at 300 K are 4.50, 3.71, 3.57, and 3.92 cm K mol per Ni
1 − 0.887x + 0.586x
3
2
2
(
1)
~
unit in a 1D metal cluster chain (Figure 1, circle inset) for Ni-
MOF-74-ac, Ni-MOF-74-IM-10, Ni-MOF-74-IM-38, and Ni-
MOF-74-IM-70, respectively. These values are higher than the
where x1,2 = J /k T, J is the coupling strength, g is the
1,2
B
1,2
1,2
Lande
́
g factor, and k is the Boltzmann constant. The best-fit
B
analysis is summarized in Table S1.
This confirms that there were changing interactions between
the Ni centers. The AFM interaction appears to be reduced
II
and the FM interaction increased by the addition of more IMs.
́
The values of the Lande g factors support the theory of a
change from 5-fold-coordinated to 6-fold-coordinated Ni ions
due to increasing amounts of IMs in the MOF. The magnetic
configuration change is also verified by these fitting results.
The magnetic ground state of Ni-MOF-74-ac was initially
AFM for the interchain and FM for the intrachain.
Interestingly, the magnetic ground state then changed to the
FM state for both interchain and intrachain Ni atoms in the
presence of IMs. Density functional theory (DFT)-calculated
results also support the idea that the magnetic phase transition
was enabled by IMs (Table S2).
The field-dependent magnetizations of Ni-MOF-74-IMs,
measured at the various temperatures, confirm the appearance
of the AFM ground state and spin-canting behavior. The M−H
curves at 2 K (Figure 3) display obvious sigmoidal shapes,
typical of the metamagnetism phase transition from AFM to
spin canting or of the FM-ordered phase as spontaneous
Figure 2. Temperature dependence of χ T measured in an applied
field of 1 kOe on powder samples of Ni-MOF-74-ac, Ni-MOF-74-IM-
m
26,27
magnetization.
As shown in Figures 3 (bottom right inset)
1
0, Ni-MOF-74-IM-38, and Ni-MOF-74-IM-70. Inset: Temperature
dependence of the magnetic susceptibility, χm (ZFCFC), of all
samples between 2 and 40 K under 1 kOe.
and S8, significant hysteresis loops are observed in the field
range of 30−55 kOe in Ni-MOF-74-ac, Ni-MOF-74-IM-10,
B
DOI: 10.1021/acs.inorgchem.9b00889
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
Figure 3. Field dependence of the magnetic moment at 2K of all
samples. Left-top inset: dM/dH from the M−H measurement. Right-
bottom inset: Metamagnetism in Ni-MOF-74-IM-10 and Ni-MOF-
Figure 4. Magnetic phase diagram of the Ni-MOF-74-IM series. The
dashed/open and line/solid points are from the M−H curves at
various temperatures. Open scattering is the critical temperature (T )
7
4-IM-38. The Ni-MOF-74-ac sample also shows metamagnetism at
N
from the M−T curves.
lower field.
and Ni-MOF-74-IM-38 (Ni-MOF-74-IM-70 does not show
metamagnetism in the M−H curve). The M values of Ni-
MOF-74-ac, Ni-MOF-74-IM-10, and Ni-MOF-74-IM-38 in-
creased to a value of ∼3.39 μB at 70 kOe, while the
that Ni-MOF-74-IMs possess an AFM ordering at the ground
state, below the phase boundary. An anomaly standing field
read for spin canting occurred at ∼30 kOe (dashed/open
points in Figure 4). The hysteresis loops in the M(H) curves
exist only at low temperatures, up to ∼10 K. The observed
irreversibility implies that the field-induced FM phase has a
tiny area of hysteresis and is metastable under high fields. The
hysteresis ranges were also changed by the amount of
coordinated IM on the OMS. Above the magnetic saturated
magnetization of Ni-MOF-74-IM-70 was 4.67 μ at 70 kOe;
B
II
this did not reach the saturation value of 6 μ for Ni with S =
B
3
(g = 6 Nβ). Although the spin centers interact, showing FM
S
interaction in a high field, they are not fully saturated because
of an orbital contribution. As the remnant spontaneous
magnetization, extrapolation of the M−H curve in the high
magnetic field range down to the zero field is taken to be an
estimate of the canting angle α, following the relationship sin α
field at ∼65 kOe (line/solid points in Figure 4) and the Nee
́
l
temperature, paramagnetic phase states were present.
The spin dynamics of Ni-MOF-74-ac and Ni-MOF-74-IMs
were further studied with alternating-current (ac) susceptibility
measurement under 1 and 65 kOe below 22 K (Figures S12−
S14). Ni-MOF-74-ac, Ni-MOF-74-IM-10, and Ni-MOF-74-
IM-38 exhibited AFM ordering, which was verified by the
frequency-independent peaks of the in-phase (χ′) at ∼18 K.
The frequency-dependent out-of-phase (χ′′) behavior in the ac
susceptibility under 1 kOe is shown. The peak temperature
=
M /M . The canting angle of Ni-MOF-74-ac was determined
R S
to be 2.2−2.5°, whereas the canting angles of Ni-MOF-74-IM-
0 and Ni-MOF-74-IM-38 were negligibly small because of
AFM interaction. The canting angle of MOF-74-IM-70
1
2
8,29
increased to 24° with FM interaction.
By increasing the
number of coordinated IMs in the channel, the hysteresis loop
and critical field are shifted to higher field. As a result, the
values of the critical field (H ) at 2 K were estimated as the
maximum field of dM/dH to be 42 kOe (Ni-MOF-74-ac), 52
kOe (Ni-MOF-74-IM-10), and 54 kOe (Ni-MOF-74-IM-38)
(T ) shift is inferred to be superparamagnetic with the Mydosh
Cr
P
parameter ϕ = ΔT /(T Δ log f) (see Figure S14 for details).
p
p
Even though MOF-74 is a 1D chain structure, it does not
actually show the slow relaxation of the SCM. Nevertheless,
the ac susceptibility results confirm that its magnetic phase is
strongly influenced by the external field and/or coordinated
imidazole.
(
inset top left in Figure 3). These hysteresis loops of the
metamagnetism and spin canting vanished above 12 K.
Moreover, the temperature dependence of χ was measured
m
to be higher than the critical field (H ), namely, 45, 55, 60,
Cr
In conclusion, this study details a novel three-dimensional
MOF, consisting of FM Ni 1D chains with coordinated IMs.
II
Such results demonstrate that Ni-MOF-74-ac and Ni-MOF-74-
IM-10 seem to exhibit the AFM effect with cusps, but the final
fitting results of the Curie−Weiss law indicate weak FM
Detailed magnetic measurements revealed the rare coexistence
of AFM and FM ordering, spin canting, field-induced
metamagnetism, and spin dynamics. Significantly, Ni-MOF-
74 exhibits phase transition and metamagnetism with IMs,
behavior with positive T values. This FM configuration of the
C
samples in the M−T curve above H verifies the existence of
accompanied by a shift in H , the Neel temperature, and the
́
cr
Cr
metamagnetism with M−H curves. Hence, the AFM coupling
was overcome, and the metamagnetism transition finally
occurred because of an external field.
Weiss temperature for AFM ordering. Indeed, the coordinated
II
IM influences the Ni coordination from the square-pyramidal
5-fold structure to an octahedral 6-fold structure. The 5-fold-
coordinated Ni has two unpaired electrons, which forces it to
transfer its magnetic phase from the AFM to FM phase with
lower energy. Interpretations made using DFT calculations and
fitting data indicate that the material studied here could be
fine-tuned for interchain magnetic interaction, and its physical
II
Phase diagrams of the metamagnetic transitions were
obtained from a series of field-dependent magnetization
M(H) curves at various temperatures and temperature-
dependent susceptibility χ(T) at different dc fields (Figures
S8−S10). The H−T phase diagram shown in Figure 4 reveals
C
DOI: 10.1021/acs.inorgchem.9b00889
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
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ASSOCIATED CONTENT
■
*
S
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b00889.
(12) Liu, K.; Zhang, X.; Meng, X.; Shi, W.; Cheng, P.; Powell, A. K.
Constraining the coordination geometries of lanthanide centers and
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AUTHOR INFORMATION
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(15) Farrusseng, D.; Aguado, S.; Pinel, C. Metal−Organic
Frameworks: Opportunities for Catalysis. Angew. Chem., Int. Ed.
Corresponding Authors
E-mail: sgkang@ulsan.ac.kr (S.G.K.).
E-mail: hoirimoon@unist.ac.kr (H.R.M.).
E-mail: oh@gntech.ac.kr (H.O.).
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range magnetic order in metal−organic frameworks. Chem. Commun.
ORCID
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014, 50, 13990−13993.
Sung Gu Kang: 0000-0003-1112-7077
Hoi Ri Moon: 0000-0002-6967-894X
Hyunchul Oh: 0000-0001-6258-0002
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Author Contributions
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S.G.K. DFT calculations, J.Y.K., H.R.M. materials synthesis,
and K.S, G.S, H.O. characterizations. The manuscript was
written through contributions of all authors. All authors have
given approval to the final version of the manuscript.
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Solvent-modulated metamagnetism in a nickel(ii) coordination
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The authors declare no competing financial interest.
2
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ACKNOWLEDGMENTS
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■
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with High Spin Magnetic Units: A Route to High Temperature
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This work was supported by National Research Foundation of
Korea grants funded by the Government of Korea (Grants
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