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org/IC Article

Water Molecule-Induced Reversible Magnetic Switching in a Bis-

Terpyridine Cobalt(II) Complex Exhibiting Coexistence of Spin
Crossover and Orbital Transition Behaviors
Fumiya Kobayashi, Yuki Komatsumaru, Ryohei Akiyoshi, Masaaki Nakamura, Yingjie Zhang,
Leonard F. Lindoy, and Shinya Hayami*
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sı Supporting Information

ABSTRACT: The development of molecule-based switchable

materials remains an important challenge in the field of molecular
science. Achievement of a structural phase transition induced by
adsorption/desorption of guest molecules in spin crossover (SCO)
Co(II) compounds is of significant interest because of the
possibility that the spin state of the magnetic anisotropic high-
spin (HS, S = 3/2) and low-spin (LS, S = 1/2) states can be
switched via the induced changes in associated intermolecular
interactions. In this study, we demonstrated a reversible magnetic
switching associated with spin state conversion, along with a single-
crystal to single-crystal (SCSC) phase transition induced by
dehydration/rehydration. [Co(terpy)2](BF4)2·H2O (1·H2O; terpy
= 2,2′:6′,2′′-terpyridine) assembles in the solid state via π−π and
CH−π interactions involving adjacent terpyridine cores along the ab direction to form two-dimensional (2D) layered domains. 1·
H2O exhibits gradual and incomplete SCO, from fully HS to ca. 0.5 HS, and the field-induced single-molecule magnet (SMM)
behavior attributed to the presence of the anisotropic partial high-spin Co(II) species. 1·H2O undergoes a SCSC transformation
accompanied by a change from the tetragonal space group I41/a to P42/n via a dehydration process. Dehydrated 1 exhibits a reverse
thermal hysteresis behavior (T1/2↑ = 287 K; T1/2↓ = 270 K) in the gradual SCO region from fully HS to ca. 0.5 HS, followed by an
ordinary thermal hysteresis (T′1/2↑ = 195 K; T′1/2↓ = 155 K) to fully LS Co(II). A temperature-dependent single-crystal X-ray
structural analysis revealed that the reverse hysteresis can be attributed to an order/disorder structural phase transition of the BF4−
anions involving a symmetry breaking to yield the monoclinic space group P21/n and orbital (angular momentum) transition (LT).
Both the SCSC phase transition and magnetic behavior are switchable by dehydration/rehydration processes; thus 1 again adsorbs
water at room temperature to give both the original structure and its magnetic behavior.

■ INTRODUCTION
Numerous bistable ferromagnetic and ferroelectric compounds
cooperativity and influence whether abrupt or thermal
hysteresis occurs.11,12
have now been reported,1,2 with interest in such compounds The acquirement of the structural dimensionality is one of
arising from their potential application in a number of areas the appropriate approaches leading to exhibit the cooperative
that include molecular sensing and information storage. Spin SCO phenomena. Increasing dimensionality in the complex
transition compounds may exhibit multistabilities under two or structure normally leads to increased cooperativity, giving rise
more conditions. Spin crossover (SCO) is characterized by a to multistable phenomena in some cases. Thus, multidimen-
transformation between high-spin (HS) and low-spin (LS) sional compounds like flexible MOFs that are able to absorb
states induced by external stimuli such as temperature, guest molecules often display multistable states that depend on
pressure, or light.3−10 Since spin state transitions in metal the presence of the guests.13−17 While multistep SCO is most
complexes also affect the latter’s optical, magnetic, and
dielectric properties, the control of spin state can be employed Received: March 18, 2020
to switch the physical properties. The SCO phenomenon is
influenced not only by the primary molecular structure of the
complex but also by the lattice packing mode and the presence
of intermolecular interactions (such as, hydrogen bonding,
CH−π and π−π interactions), which act to enhance

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.inorgchem.0c00818

A Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry pubs.acs.org/IC Article

Figure 1. Single-crystal structures (including disordered BF4− anions) of (a) 1·H2O and (b) 1. The light blue dashed lines represent hydrogen
bonds. (c) Packing view of 2D layered structure along the c axis of 1·H2O and 1. In the packing view, all hydrogen atoms, counteranions, and water
molecules are omitted for clarity. Color code: H, white; B, pink; C, gray; N, blue; O, red; F, yellow; Co, magenta.

likely observed for multidimensional compounds, it also occurs
for mononuclear complexes displaying enhanced cooperative-
ness through the presence of strong intermolecular interactions
with adjacent molecules.18−22 Unlike MOFs, mononuclear
complexes exhibiting multifunctionality tend to be less
responsive to the reversible adsorption/desorption of guest
species with keeping their crystallinity due to their generally
more rigid structures. Few mononuclear complexes are known
that are reversibly converted to multistable states with single-
crystal to single-crystal (SCSC) transition in response to the
uptake of guest species.23−30
Herein, we report new examples of water molecule-induced
reversible switching of multistep magnetic behavior along with
a “cross loop” type hysteresis that involves both reverse and
normal thermal hysteresis. This occurs for the mononuclear
Co(II) complex [Co(terpy)2](BF4)2·H2O (1·H2O, terpy =
2,2′:6′,2′′-terpyridine), which also exhibits single-molecule
magnet (SMM) behavior, as well as for its desolvated
[Co(terpy)2](BF4)2 (1) complex. Although these properties
suggest the prospect of forming new switching materials that,
for example, switch between SCO and SMM behaviors, there
appears to be only one reported example of this so far.31
B https://dx.doi.org/10.1021/acs.inorgchem.0c00818
Although the SMM behavior is not usually observed in six-
coordinated Co(II) SCO complexes because the LS Co(II)
species lack the magnetic anisotropy, in the present study, the
switch of SMM behavior has been achieved by the spin state
conversion between HS and LS states induced by the reversible
adsorption/desorption of the lattice water molecules. Mono-
nuclear Co(II) complexes are unusual in that they character-
istically show high responsivity to a slight change in their
intermolecular interactions that can be attributed to their lower
spin entropy (ΔSspin = R[ln(2S + 1)HS − ln(2S + 1)LS] = 5.8 J
K−1 mol−1),32 occasionally leading to them exhibiting unique
SCO behavior such as a reverse spin transition.33−35 In
addition, a high orbital angular momentum (L) contribution in
HS Co(II) complexes can lead to orbital quenching and
unique hysteretic behaviors such as reported by Juhász et al.36
As opposed to SCO driven by entropy change, such transition
of the orbital angular momentum (orbital transition, LT) is
mainly caused by structural transition that includes the
symmetry change of the coordination sphere. However, the
examples of LT are quite limited because the orbital angular
momentum of most first-row transition metal complexes is
usually small, and in most cases, the detailed mechanism of
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
such unique LT and hysteretic behaviors remains unclear. In
contrast, in the present study, we have succeeded in elucidating
the origin of the cross loop hysteresis attributed to an LT
triggered by an order/disorder structural phase transition of
the BF4− anions by analyzing the crystal structures before and
after the observed phase transition.
■ EXPERIMENTAL SECTION
Synthesis. All chemicals were purchased from commercial sources
and used without further purification.
[Co(terpy)2](BF4)2·H2O (1·H2O; terpy = 2,2′:6′,2′′-terpyri-
dine). Co(BF4)2·6H2O (74 mg, 22 mmol) in acetone (10 mL) was
added to a solution of 2,2′:6′,2′′-terpyridine (100 mg, 43 mmol) in
acetone (10 mL). The solution immediately turned brown. Water (3
mL) was added, and the solution was allowed to slowly evaporate to
give the product as dark brown crystals. Elemental analysis for
C30H24B2CoF8N6O: Calc. C, 50.25; H, 3.37; N, 11.72%. Found. C,
50.50; H, 3.57; N, 11.76%. The TGA curve showed 2.6% weight loss
at 400 K. This shows good agreement with the water molecule
content expected for 1·H2O (H2O = 2.5%). IR (νmax, cm−1) 3645,
3568, 3114, 1601, 1473, 1452, 1400, 1321, 1288, 1243, 1163, 1103,
1052, 1025, 767, 648, 520.
Dehydrated [Co(terpy)2](BF4)2 (1). For the single-crystal
structural analysis, a single crystal of 1·H2O was dehydrated to give
(dehydrated) 1 by heating at 333 K for 1 h in the SCXRD system. For
the other physical measurements, the crystalline sample of 1·H2O was
dehydrated to give dehydrated 1 by heating at 400 K for 1 h in the
measuring instruments (such as the SQUID or DSC system).
Rehydrated [Co(terpy)2](BF4)2·H2O (1·reh). The crystalline
sample of 1 was left to stand for 1 day in air at room temperature
(ca. 25 °C) to give the rehydrated product. Elemental analysis for
C30H24B2CoF8N6O: Calc. C, 50.25; H, 3.37; N, 11.72%. Found. C,
50.42; H, 3.45; N, 11.61%. The TGA curve showed 2.7% weight loss
at 400 K.
Physical Measurements. Single-crystal X-ray data for 1 and 1·
H2O were recorded with an Oxford Gemini Ultra diffractometer
employing graphite monochromated Mo−Kα radiation generated
from a sealed 261 tube (λ = 0.7107 Å). Data integration and
reduction were undertaken with CrysAlisPro. Using Olex2, the
structure was solved with the SHELXT structure solution program
using Direct Methods and refined with the SHELXL refinement
package using Least Squares minimization. Hydrogen atoms were
included in idealized positions and refined using a riding model. The
single-crystal X-ray diffraction measurements for 1 at 223 and 100 K
were carried out on the MX2 beamline at the Australian Synchrotron.
Diffraction data were collected using Si ⟨111⟩ monochromated
synchrotron X-ray radiation (λ = 0.71074) at 100(2) K with BlueIce
software and were corrected for Lorentz and polarization effects using
the XDS software. The structure was solved with SHELXT, and the
full-matrix least-squares refinements were carried out using SHELXL-
2014 via the Olex2 interface. All non-hydrogen atoms with
occupancies over 0.5 were located from the electron density maps
and refined anisotropically. Hydrogen atoms bound to carbon,
nitrogen, and oxygen atoms were added in the ideal positions and
refined using a riding model. Temperature-dependent direct-current
(dc) magnetic susceptibilities for crystalline samples of 1·H2O and 1
were measured on a Superconducting Quantum Interference Device
(SQUID) magnetometer at a field strength of 5000 Oe with a sweep
mode of 2 K min−1 in the temperature range 5 to 400 K. Elemental
analyses (C, H, N) were carried out at the Instrumental Analysis
Centre of Kumamoto University. Differential scanning calorimetry
(DSC) thermal analysis for 1 was carried out at 10 K min−1 on a
SHIMADZU DSC50.
■
RESULTS AND DISCUSSION
Structural Characterization. The crystal structures of 1·
H2O and 1 were solved by variable-temperature single-crystal
X-ray diffraction (VT-SCXRD) measurements at 123 and 333
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K, respectively (Table S1). 1·H2O crystallized in the tetragonal
space group I41/a. Several polymorphs of 1·H2O were
obtained; however, the use of an acetone/water mixture for
crystallization led to isolation of a single morphology (see the
Experimental Section and Figure S1). In contrast to the
present case, Kilner and Halcrow have reported that the use of
nitrobenzene as a solvent during crystallization leads to
isolation of only the nonsolvated compound [Co(terpy)2]-
(BF4)2.37 The molecular structure of this product is shown in
Figure 1a. Two tridentate meridional terpyridine ligands yield
an octahedral coordination environment, with one lattice water
molecule and two BF4− counterions being present. The
respective Co−N distances are Co−N1 = 2.124 Å, Co−N2
= 1.989 Å, Co−N3 = 2.118 Å, and Co−N4 = 1.990 Å. The
bond lengths are consistent with those of typical HS Co(II)
compounds.7,31,36 Selected bond lengths for 1·H2O are
summarized in Table S2. The distortion parameters Σ for
the [CoN6] core were calculated; Σ is the sum of |90−α| for
the 12 cis-N−Co−N angles.38,39 Σ for 1·H2O is 108.48 (Table
S3), indicating high distortion at low temperature compared to
other reported LS state bis-terpyridine Co(II) compounds.37,40
Each water molecule in the crystal packing structure forms
hydrogen bonds with two neighboring BF4− ions (Figure S2).
The respective intermolecular hydrogen bond distances are B−
F1A···O8 = 2.927 Å, B−F2A′···O8 = 2.584 Å, B−F3′···O8 =
3.266 Å, and B−F4′···O8 = 3.062 Å. These hydrogen bonds
result in anion layers along the ab direction, with the lattice
water molecules being located in the resulting cavities (Figure
S3a,c). The two terpyridine moieties in 1·H2O are assembled
with π−π (N1−C5; N3−C13: centroid−centroid distance
3.679 Å) and CH−π (H2, H10; N1−C5, N3−C13: H−
centroid distance 2.953 Å, 2.974 Å) interactions with their
adjacent cores oriented along the ab direction; these are
layered in the ab plane with infinite π−π and CH−π stacking
interactions present. Each layer is separated by BF4− anions;
there are no direct interactions between each layer (Figure 1c).
1·H2O was dehydrated to give 1 by heating at 333 K for 1 h;
the hydration process was also followed by thermogravimetric
analysis (TGA) (Figure S4a). On letting dehydrated 1 stand in
the atmosphere, the water molecules were spontaneously
reabsorbed at room temperature to produce the original 1·
H2O. Multiple repetition of the dehydration/rehydration
process using TGA was also in accord with this result (Figure
S4b).
VT-SCXRD measurement on the dehydrated product 1 was
conducted at 333 K in order to compare its structure with that
of 1·H2O. In the former, the space group had changed to the
tetragonal space group P42/n at 333 K; the crystal structure is
shown in Figure 1b. The BF4− anions in 1 are heavily
disordered due to the absence of structural restriction by
hydrogen bonding compared with those present in 1·H2O
(Figure S2). The Co−N distances are Co−N1 = 2.127 Å and
Co−N2 = 2.015 Å, with these bond lengths being consistent
with those for typical HS Co(II) compounds. The Σ value for
1 is 118.4, indicating higher distortion than that for 1·H2O. 1 is
also assembled in the crystal lattice via intermolecular π−π
(N1−C5; N1′−C5′: centroid−centroid distance 3.736 Å) and
CH−π (H4; N1−C5: H−centroid distance 3.003 Å)
interactions as occur in 1·H2O (Figure S3b,d). Reflecting the
strong lattice interactions present, the crystal packing structure
maintained the crystal void observed in the unit cell of 1·H2O,
with the dehydrated derivative giving an increased value Δ =
19.65 Å3 per Co(II) cation (Figure S5). The absorption/
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
desorption process observed for the water molecule in
crystalline 1·H2O is also synchronized with the reversible
single-crystal to single-crystal (SCSC) phase transition. The
powder X-ray diffraction (PXRD) patterns for 1·H2O and
dehydrated 1 as well as for the rehydrated complex from 1 (1·
reh) are shown in Figure S6. The PXRD patterns for 1·H2O
and dehydrated 1 are slightly different; reversible changes in
the RXRD patterns between 1 and 1·reh were also observed.
Magnetic Behavior of 1·H2O. The temperature depend-
ence of magnetic susceptibility for crystalline samples of 1·H2O
was measured employing a Superconducting Quantum
Interference Device (SQUID). The corresponding χmT versus
T curves, where χm is the molar magnetic susceptibility and T
is the temperature, are shown in Figure 2. At 350 K, the χmT
Figure 2. χmT versus T plots for 1·H2O (black) and 1 (red, blue)
collected under an applied field of 5000 Oe.
value of 2.11 cm3 K mol−1 is higher than the spin-only χmT
value for one high-spin Co(II) ion (S = 3/2, 1.875 cm3 K
mol−1), indicating an orbital angular momentum contribution.
On lowering the temperature, the χmT value for 1·H2O
gradually decreased from 2.11 at 350 K to 1.14 cm3 K mol−1 at
5 K, which represents incomplete SCO behavior for Co(II) in
an octahedral environment and reflects the highly distorted
structure present at low temperature. This SCO behavior
corresponds to the presence of 1/2 HS (S = 3/2, 1.875 cm3 K
mol−1) and 1/2 LS (S = 1/2, 0.375 cm3 K mol−1) species, i.e., a
[HS-LS] phase. On heating the sample from 5 to 350 K, the
same SCO behavior was observed.
Bis-terpyridine Co(II) complexes having highly distorted
octahedral high-spin Co(II) centers sometimes exhibit slow
magnetic relaxation behavior as is expected for SMMs due to
their large magnetic anisotropy.31,41 For 1·H2O, variable-field
magnetization plots show saturation behavior at 1.73 μβ under
an applied field of 5 T at 2 K (Figure S7). The expected
magnetization value for 0.5 HS and 0.5 LS of a spin-only
Co(II) ion is 2 μβ, with derivation from this value arising from
the presence of the magnetic anisotropy of the HS species.
That saturation behavior in 1·H2O is observed at a lower value
than 2 μβ indicates the presence of a highly anisotropic ground
state. Their large magnetic anisotropy leading to slow magnetic
relaxation were demonstrated by also variable-field alternating
current (ac) susceptibility measurements. In order to
investigate possible slow magnetic relaxation behavior in 1·
H2O, variable-field ac susceptibility measurements for 1·H2O
were performed at 1.9 K under applied fields of between 0 and
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5000 Oe (Figure S8). The in-phase (χm′) and out-of-phase
(χm″) components exhibited no frequency dependence under
zero applied dc field. The absence of slow magnetic relaxation
under zero applied field is in accord with the occurrence of
quantum tunneling of the magnetization (QTM) as occurs
with many other mononuclear Co(II) SMMs. The frequency
dependence of the χm′ and χm″ components becomes
significantly more intense with the application of an external
dc field, revealing slow magnetic relaxation behavior as
expected for SMMs. As the applied field is increased, one
relaxation pathway begins to appear at above ∼1500 Hz and
increases in intensity until 1000 Oe, after which it begins to
decrease. A second relaxation pathway appears between 1 and
10 Hz under an applied dc field of 1500 Oe; it appears initially
as a shoulder and then reaches a full peak as the applied field
increases. A peak in χm″ was evident under the applied external
fields, with a maximum shift to low frequencies being observed
for the 5000 Oe (dc) field, which we consider as the optimal
field for observing slow magnetic relaxation. Under applied
fields of 500 and 5000 Oe (where only one relaxation pathway
is clearly dominant), the χm″ versus frequency plots reveal clear
temperature-dependent peaks down to 1.9 K (Figures 3, S8,
S9, and S11). The occurrence of two such relaxation pathways
in other mononuclear Co(II) SMMs has frequently been
observed42−45 and attributed to the presence of the spin−spin
interactions caused by intermolecular short contacts, such as
hydrogen bonds, π−π stacking, and CH−π interactions−
resulting in much slower spin relaxations than occur in pure
mononuclear entities. The origin of the second main group of
such a spin relaxation process has been investigated by using
magnetic dilution of a seven-coordinate mononuclear Co(II)
complex, [Co(DAPBH)(NO3)(H2O)](NO3) (DAPBH = 2,6-
diacetylpyridinebis(2′-pyridylhydrazone)) which shows the
field-induced SMM behavior, with the diamagnetic Zn(II)
analogue by Habib and co-workers.46 The observed second
relaxation step decreases with the dilution. Such a magnetic
dilution study using a diamagnetic ion reveals the influence of
the intermolecular interactions on the relaxation processes in
mononuclear SMMs. Ceglarska and co-workers also have
reported very recently that the creation of the two frequency
domains observed in a six-coordinated Co(II) SMM
[CoBr2(pyridine)2] is of intermolecular origin by using a
similar systematic study of magnetic dilution.47 These studies
clearly indicate that the occurrence of multiple relaxation
pathways is attributed to the presence of intermolecular
interactions.
In order to elucidate the relative contributions of the two
relaxation pathways, the temperature-dependent relaxation
times for applied fields of 500 and 5000 Oe were determined
by fitting the out-of-phase susceptibility using the generalized
Debye model (Figures S10 and S12).48,49 For the Cole−Cole
analysis, the α values are considerably smaller, falling in the
range of 0.001−0.06 for 5000 Oe and 0.22−0.24 for 5000 Oe,
suggesting the presence of a single relaxation process (Table
S4). To extract the relaxation time and spin reversal barrier,
the maximums of the out-of-phase χm″ values from the
temperature-dependent data were used to construct the
Arrhenius plots given in Figure S13. In these ln(τ) vs T−1
plots, linear data corresponding to the Arrhenius law τ = τ0
exp(Ueff/kBT) were obtained, with an effective energy barrier
of Ueff = 4.2 K (τ0 = 1.1 × 10−5 s) and 3.6 K (τ0 = 1.1 × 10−2 s)
for the fast and slow relaxation processes, respectively. These
values are similar to those obtained for other reported Co(II)
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 3. Variable-frequency out-of-phase (χm″) components of the
ac susceptibilities for a crystalline sample of 1·H2O collected under an
applied dc field of (a) 500 Oe and (b) 5000 Oe. The solid lines
represent the best fits of the experimental results for the generalized
Debye model.
complexes.50,51 The relaxation mechanisms for a mononuclear
single-molecule magnet system are usually very complex and
involve multiple relaxation pathways. Although up to four
possible relaxation mechanisms (QTM, direct, Raman, and
Orbach processes) may usually occur, the QTM should, in
principle, be suppressed in the case of measurements under an
applied dc field. When a relaxation process other than the
Orbach process may play a role, or that there is more than one
thermally activated relaxation process occurring, then the ln(τ)
vs T−1 plots will show a departure from Arrhenius behavior.
For the type of Kramers ion incorporating Co(II), the main
contribution of such a slow magnetic relaxation is a
combination of a direct mechanism and the Raman
process.52,53 In the present study, a clear departure from
Arrhenius behavior was not observed in the measured
temperature region, indicating that a Raman process is not a
main contributor to the slow magnetic relaxation observed for
this system. However, in the present study we need to point
out that the obtained τ values are only rough estimations.
Further measurements spanning a higher frequency range (ν >
1500 Hz) or a lower temperature region are required to obtain
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the precise values for other relaxation mechanisms for both
relaxation pathways.
Magnetic Behavior of 1. The dehydrated compound 1
was obtained by annealing polycrystalline samples of 1·H2O at
400 K for 1 h in the SQUID system. On lowering the
temperature, the χmT value of 1 gradually decreased from 2.22
at 400 K to 1.58 cm3 K mol−1 at 274 K, indicating thermal
SCO behavior, and it then slightly increased to 1.66 cm3 K
mol−1 at 264 K (T′1/2↓ = 270 K). This increase may be
rationalized in terms of a reverse spin transition or an angular
momentum quenching as reported for several Co(II) and
Fe(II) complexes.33−35,54−56 Upon further cooling, χmT
abruptly decreased from 0.89 at 161 K to 0.47 cm3 K mol−1
at 142 K (T1/2↓ = 155 K) following the initial linear decrease of
the χmT value. The χmT value for 1, 0.40 cm3 K mol−1 at 5 K, is
consistent with the presence of LS Co(II) (S = 1/2) in an
octahedral environment. Upon heating, the χmT value
gradually increased from 0.44 at 146 K to 0.69 cm3 K mol−1
at 192 K and then abruptly increased to 1.15 cm3 K mol−1 at
203 K (T1/2↑ = 195 K). On further heating, the χmT value
decreased slightly from 1.83 at 283 K to 1.81 cm3 K mol−1 at
297 K (T′1/2↑ = 287 K). The values of T1/2↑ and T1/2↓ and
T′1/2↑ and T′1/2↓ for the heating and cooling cycles correspond
to thermal hysteresis loops with ΔT = 40 K and ΔT′ = 17 K,
respectively. Although such a “cross loop” hysteresis, including
the reverse and ordinary thermal hysteresis loops, has been
reported previously by Agusti et al. for [Co(4-terpyridone)2]-
(CF3SO3)2·H2O, the mechanism involved still remains
unclear.57 As a scan rate is increasing, both reverse and
normal thermal hystereses become wider. The observed
thermal hysteresis loops at a scan rate of 5 K min−1 were
ΔT = 51 K and ΔT′ = 34 K, respectively (Figure S14, Table
S5). Although this is usually reflected in the thermalization
process of the samples, it seems that the observed reverse
thermal hysteresis is more sensitive to the scan rate compared
with the normal thermal hysteresis at low temperature. In
order to confirm the presence of slow magnetic relaxation,
variable-field ac susceptibility measurements for 1 were also
performed at 1.9 K under applied field strengths between 0 and
3000 Oe (Figure S15). The out-of-phase (χm″) components
exhibited no frequency dependence even under an applied dc
field of 3000 Oe. The observed magnetic behavior indicates no
presence of slow magnetic relaxation for 1, reflecting the
presence of LS Co(II) species which lack the magnetic
anisotropy exhibited by HS Co(II) species. Dehydrated 1
reabsorbed water at room temperature to again yield 1·H2O
(which exhibited the same SCO and SMM behaviors as the
original hydrated product).
Differential Scanning Calorimetry and Crystallo-
graphic Study of 1. Differential scanning calorimetry
(DSC) measurement and further crystallographic studies at
223 and 100 K were performed in order to further probe the
two hysteric behaviors observed for 1. Following the initial
thermal treatment of polycrystalline samples of 1·H2O at 400
K for 1 h to produce 1, DSC curves were obtained for the
product in the range 120 to 400 K (Figure S16, Table S6).
Two exothermic peaks were observed at ca. 265 and 170 K,
respectively, during the cooling process; these correspond to
T′1/2↓ and T1/2↓ for the spin transition. Two endothermic peaks
were observed at around 200 and 275 K thus confirming the
reversible nature of the phase transition in 1.
VT-SCXRD measurements for 1 at 223 and 100 K were
performed at the Australian Synchrotron (Figure 4). During
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry pubs.acs.org/IC Article

Figure 4. Asymmetric unit and comparison of the [CoN6] coordination bond lengths for 1 at (a) 333 K and (b) 223 K. The BF4− anion is
disordered at 333 K.

Figure 5. Schematic representation of the order/disorder structural phase transitions in 1. The disordered BF4− anions at 333 K are ordered at 223
K.

the cooling process from 333 K, 1 gave rise to the structural
phase transition with the exothermic peak at ca. 265 K. At 223
K, it is in the intermediate state as shown by the χmT versus T
curves (and associated with the reverse χmT changes reflecting
the structural phase transition). Symmetry breaking was
observed along with the space group change to the monoclinic
space group P21/n; the crystal structure and packing structure
are shown in Figures S17 and S18. The observed satellite
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reflections at 223 K yielded a doubling of the lattice parameter
along the stacking direction, and consequently, the b
parameter, 38.398(8) Å at 233 K, is almost double the value
obtained at 333 K, namely 19.507(2) Å; that is, the volume of
the unit cell changes from 1517.5(3) to 2981.2(10) Å3 (Table
S7). The phase transition accompanying the change in the cell
parameters in this intermediate phase is in accord with the
occurrence of an order/disorder phase transition, induced by
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 6. Comparison of the layered structure at 100 K of (a) 1 and (b) polymorph [Co(terpy)2](BF4)2.37
two independent BF4− counteranions in the interlayer space,
leading to crystallographically distinct anion layers (Figure 5).
The resulting structural ordering is characteristic of the
intermediate state of mononuclear complexes and 2D MOFs
exhibiting multistep SCO behaviors.14,19,57−62
The changes in the cell parameters generated for the
intermediate phase were observed to remain (at ∼170 K) even
after the phase transition has occurred during the cooling
process. The cell parameters at 100 K are doubled relative to
those present at 333 K, and two different lattice layers are
present, even for the complete LS state (Figure S18a). This
seems to imply that the formation of the two crystallo-
graphically independent alternating anion layers in the
intermediate state led to abrupt spin transition to the LS
species. The thermal variation of the cell parameters for 1
derived from quick scans resulted in a small change in the in-
plane direction, while the length of the out-of-plane direction
increased with the increasing temperature (Figure S19). The
rigidity of the layer structure in the in-plane is aided by the
presence of π−π and CH−π interactions between [Co-
(terpy)2]2+ units, while the interlayer structure is influenced
to some degree by the thermal vibrations of the BF4− anions.
The cell parameters observed at high temperature were
restored during the heating process, once again confirming
the reversibility of the structural phase transition.
The selected bond lengths and the distortion parameters Σ
for 1 at 223 and 100 K are summarized in Tables S8 and S9,
respectively. At 100 K, although the average Co−N distance of
2.040 Å and the Σ value of 95.6 are higher than those of other
LS Co(II) complexes, the ΔΣ value of 22.8 for 1 between HS
and LS is a typical value observed for SCO Co(II) complexes.
As reported in our previous study, the structural distortion of
the [CoN6] core is a dominant factor leading to abrupt spin
transition in hexacoordinated Co(II) complexes.40 Reflecting
the highly distorted structure and the in-plane high
cooperativity attributed to the strong intermolecular inter-
G https://dx.doi.org/10.1021/acs.inorgchem.0c00818
pubs.acs.org/IC Article
actions, and 1 exhibits an abrupt spin transition with wide
thermal hysteresis. The average Co−N distance and the Σ
value at 223 K are 2.058 Å and 104, respectively. These are in
the middle range between HS and LS, reflecting a spin state
corresponding to the presence of 1/2 HS and 1/2 LS species.
Although the temperature range from 400 to 170 K for the
cooling process corresponds to the gradual SCO region, the
structural phase transition occurred at 265 K resulting in the
observed change of the χmT value (Figure S20). This χmT
change seems best attributed to angular momentum quenching
rather than to a reverse spin transition. It is well-known that
the contribution of the orbital angular momentum is quite
large in HS Co(II) complexes and that it is reflected in the
structural symmetry. As reported by Titiš et al., the magnetic
anisotropy in hexacoordinated Co(II) complexes correlates
with the structural distortion of the coordination polyhedron.63
The reduction in the structural symmetry in HS Co(II)
complexes leads to an increase in the contribution of the
orbital angular momentum involving an increase of the χmT
value.36 In the present case, the symmetry reduction involving
the change of asymmetric unit would be expected to lead to an
increase in the contribution of the orbital angular momentum
and in the χmT value. The entropy changes (|ΔS|) at 265 and
275 K obtained by DSC measurements are 3.356 J K−1 mol−1
and 3.467 J K−1 mol−1, respectively. These values correspond
to the reported entropy change (ΔS = 3.622 J K−1 mol−1) for
an order/disorder type transition for a BF4− anion.64 These
reversible phase transitions cause the changes that occur in the
intermolecular interactions between the [Co(terpy)2]2+ cations
and BF4− anions, resulting in the observed structural symmetry
changes and unique cross loop hysteresis. In fact, several
examples of spin transitions, including reverse spin transitions,
associated with structural transitions in metal complexes
incorporating BF4− anions have been reported previously.35,65
The formation of hydrogen bonding between water molecules
and BF4− anions induced by the hydration process clearly
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
hinders such order/disorder transition for these anions, leading
to the gradual SCO behavior observed, including the small
stepwise changes of the χmT value found for 1·H2O. Although
it seems that the similar crossed hysteretic behavior reported
by Agusti et al. for [Co(4-terpyridone)2](CF3SO3)2·H2O57 can
also be attributed to LT associated with the structural
transitions of the CF3SO3− anions rather than to a reverse
spin transition, a more detailed structural study such as one
employing VTSCXRD would be required to determine the
origin. In contrast to the observed cross loop hysteresis
occurring for 1, the polymorph [Co(terpy)2](BF4)2 reported
by Kilner and Halcrow37 exhibits gradual SCO without
structural transitions. This appears to be a reflection of the
difference arising from the presence of the stacked layered
structures rather than being the result of the intralayer
interactions. Although the cationic layers in 1 are stacked in
phase, those of the above polymorph are stacked out of phase
and associated with a different interlayer distance (Figure 6).
The different interlayer structural arrangements, in turn, lead
to different intermolecular interactions between the [Co-
(terpy)2]2+ cations and BF4− anions, which are the important
key to lead the cross loop hysteretic behaviors.
■
CONCLUSION
In summary, we have presented an example of water molecule-
induced reversible magnetic switching in a mononuclear
Co(II) complex. Thus, 1·H2O undergoes a reversible SCSC
transformation with desorption of water molecules, leading to
a change in its magnetic behavior. Monohydrate 1·H2O
exhibits gradual SCO and field-induced SMM behavior,
whereas dehydrated 1 exhibits multistep cross loop hysteretic
behavior. This cross loop hysteresis is attributed to the abrupt
spin crossover (SCO) in the low temperature region and
orbital transition (LT) in the high temperature region. In this
flexible guest-responsive system, the presence of intermolecular
interactions, such as π−π and CH−π interactions, creates
pseudodimensionality. In addition, investigation of the
influence of the angular momentum on the order/disorder
phase transition involving the BF4− counterions leads to a
deeper understanding of similar SCO systems. In addition, it
was unexpected that the observed unusual multifunctional
properties were exhibited by the “classical” bis-terpyridine
Co(II) complex. The high responsivity of the Co(II) ion,
attributed to its spin entropy, clearly warrants more attention
in future studies of the present general type. In addition, the
results presented provide the basis for new design strategies for
generating guest-responsive, multifunctional switching materi-
als as well as other unique SCO and LT systems.
■ ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00818.
Crystallographic data, PXRD, TGA, magnetic properties,
and DSC (PDF)
Accession Codes
CCDC 1903790−1903791 and 1980590−1980591 contain
the supplementary crystallographic data for this paper. These
data can be obtained free of charge via www.ccdc.cam.ac.uk/
data_request/cif, or by emailing data_request@ccdc.cam.ac.
uk, or by contacting The Cambridge Crystallographic Data
H https://dx.doi.org/10.1021/acs.inorgchem.0c00818
pubs.acs.org/IC Article
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223 336033.
■ AUTHOR INFORMATION
Corresponding Author
Shinya Hayami − Department of Chemistry, Graduate School of
Science and Technology and Institute of Pulsed Power Science
(IPPS), Kumamoto University, Kumamoto 860-8555, Japan;
orcid.org/0000-0001-8392-2382; Email: hayami@
kumamoto-u.ac.jp
Authors
Fumiya Kobayashi − Department of Chemistry, Graduate
School of Science and Technology, Kumamoto University,
Kumamoto 860-8555, Japan; orcid.org/0000-0002-6923-
6332
Yuki Komatsumaru − Department of Chemistry, Graduate
School of Science and Technology, Kumamoto University,
Kumamoto 860-8555, Japan
Ryohei Akiyoshi − Department of Chemistry, Graduate School
of Science and Technology, Kumamoto University, Kumamoto
860-8555, Japan
Masaaki Nakamura − Department of Chemistry, Graduate
School of Science and Technology, Kumamoto University,
Kumamoto 860-8555, Japan
Yingjie Zhang − Australian Nuclear Science and Technology
Organization, Kirrawee DC, New South Wales 2232, Australia
Leonard F. Lindoy − School of Chemistry, The University of
Sydney, Sydney, New South Wales 2006, Australia
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c00818
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by a KAKENHI Grant-in-Aid for
Scientific Research (A) JP17H01200. F.K. is grateful to JSPS
Research Fellowships for Young Scientists (No. JP19J11651).
This research was undertaken in part using the MX2 beamline
at the Australian Synchrotron, part of ANSTO, and made use
of the Australian Cancer Research Foundation (ACRF)
detector.
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