Weak ferromagnetism derived from spin canting in an amido-bridged homochiral Mn(iii) 1-D coordination polymer

Article abstract of DOI:10.1039/c9dt00593e

A homochiral one-dimensional (1D) Mn(iii) coordination polymer [MnL]_n (1) was synthesised employing the N₃O-donor tetradentate ligand (L = 2-hydroxy-N-[2-[[(2-aminophenyl)methylene]amino]-2-methylpropyl]-benzamide). The X-ray structu

Full text of DOI:10.1039/c9dt00593e

View Article Online
View Journal
Dalton
Transactions
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: S. Kusumoto, A.
Koga, F. Kobayashi, R. Ohtani, Y. Kim, L. F. Lindoy, S. Hayami and M. Nakamura, Dalton Trans., 2019, DOI:
10.1039/C9DT00593E.
This is an Accepted Manuscript, which has been through the
Volume 45 Number
1 7 January 2016 Pages 1–398
Royal Society of Chemistry peer review process and has been
accepted for publication.
Dalton
Transactions
Accepted Manuscripts are published online shortly after
An international journal of inorganic chemistry
www.rsc.org/dalton
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

Please do not adjust margins
Page 1 of 6
Dalton Transactions
View Article Online
DOI: 10.1039/C9DT00593E
Journal Name
ARTICLE
Weak Ferromagnetism Derived from Spin Canting in an Amido-
Bridged Homochiral Mn(III) 1-D Coordination Polymer
Sotaro Kusumoto,a Atsushi Koga,a Fumiya Kobayashi,a Ryo Ohtani,a Yang Kim,a Leonard F.
Lindoy,b
Shinya Hayami,*a,c Masaaki Nakamura*a
A homochiral one-dimensional (1D) Mn(III) coordination polymer [MnL]n (1) was synthesised employing the N3O-donor
tetradentate ligand (L = 2-hydroxy-N-[2-[[(2-aminophenyl)methylene]amino]-2-methylpropyl]-benzamide). The X-ray
structure of 1 and its magnetic properties were investigated in detail. The crystal structure of 1 shows a homochiral helical
arrangement in which spontaneous resolution has occurred, despite the ligand being achiral. Magnetic characterization
revealed an antiferromagnetic interaction between manganese(III) ions (J = 2.7 cm1, g = 1.95) that leads to an
antiferromagnetic spin-ordering phase transition at TN ≈ 7 K. Noteworthily, 1 exhibits weak ferromagnetism with a relatively
large coercive field of 3.0 kOe based on the spin canting, indicating the formation of a homochiral weak ferromagnet.
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
have also been reported.1618 While syntheses of the latter type
have the virtue of simplicity, unfortunately such spontaneous
resolution behaviour is largely unpredictable since the
associated homochiral crystal packing normally occurs
serendipitously (and hence is unable to be controlled).
Introduction
The study of molecular-based magnetic materials, such as
single-molecule magnets (SMMs), single-chain magnets (SCMs),
ferromagnets and ferrimagnets has evoked considerable
interest in chemists during past decades because each of these
categories has implications for the development of the next
generation of quantum and molecular devices.18 For example,
chiral magnetic materials that combine molecular magnetism
and optical ability have attracted much attention in view of the
development of multifunctional materials such as
magnetochiral dichromism (MChD) and multiferroic
materials.913
High-spin Mn(III) complexes are often found to behave as SMMs
or SCMs, with canted behaviour and long-range magnetic order
emerging because the Mn(III) ion has a large spin value (S = 2)
and a single-ion axis anisotropy induced by the presence of a
Jahn−Teller distortion on the octahedral geometry.1925 In prior
studies, salen-based ligands have been employed for the
synthesis of 1-D Mn(III) coordination polymers in which both
axial positions of the metal are occupied by various bridging
ligands such as azide, cyanide and phosphonate.2630 While
azide-bridged systems have been used extensively for the
construction of salen-derivative based magnetic systems,3135
amido-bridged systems are much less common. In one study of
this type, Costes and coworkers reported the synthesis and
magnetic investigation of a Mn(III) complex in which a N2O2-
donor salen derivative incorporates an amido group that acts as
a bridge between Mn(III) centers to yield a 1D-chain structure
The use of one-dimensional (1D) coordination polymers
provides
a suitable approach for the development of
multifunctional materials showing both magnetism and chirality
due to their often ease of design and high anisotropy. Most
commonly, enantiopure ligands have been employed to
introduce homochirality into coordination polymers, including
by employing chiral linkers between metal centres.1415 On the
other hand, examples of the self-assembly of chiral
coordination polymers incorporating only achiral precursors
that undergo spontaneous resolution during crystallization
showing
antiferromagnetic
interaction
and
weak
ferromagnetism due to spin canting.36
Motivated by the potential to obtain new magnetic
coordination polymers with amido-bridges, we designed the
asymmetrical
N3O-donor
ligand
2-hydroxy-N-[2-[[(2-
a Department of Chemistry, Graduate School of Science and Technology,
Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan. E-
mail: m_nakamura@kumamoto-u.ac.jp, hayami@kumamoto-u.ac.jp
b School of Chemistry, The University of Sydney, NSW 2006, Australia.
c Institute of Pulsed Power Science (IPPS), Kumamoto University, 2-39-1 Kurokami,
Chuo-ku, Kumamoto 860-8555, Japan.
aminophenyl)methylene]amino]-2-methylpropyl]-benzamide
(H3L) incorporating an amide group (Scheme 1) and synthesised
the homochiral 1-D Mn(III) complex [MnL] (1). Spontaneous
resolution of 1 occurred during crystallization from its ethanol
reaction mixture and the resulting crystalline diastereomeric
mixture, 1M/1P, was isolated (and single crystals separated –
see later). The magnetic characterization of 1 revealed the
† CCDC 1862151, 1862114. For crystallographic data in CIF or other electronic
format see DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 2 of 6
ARTICLE
Journal Name
existence of antiferromagnetic interactions, presumably
occurring via the amido-bridges linking the metal centers (J =
2.7 cm1, g = 1.95), as well as weak ferromagnetism caused by
spin canting (ordering temperature ≈ 7 K). To the best of our
knowledge, this represents the first report of homochiral Mn(III)
amido-bridged one-dimensional coordination polymers
exhibiting weak ferromagnetism.
with the shortest intermolecular chain distance between
manganese ions being 7.257 Å. Major Intermolecular
View Article Online
DOI: 10.1039/C9DT00593E
interactions such as CH-, -, etc. between the chains were
not observed. Key bond lengths in 1M, Mn(1)N(1),
Mn(1)N(2), Mn(1)N(3), Mn(1)O(1) and Mn(1)O(2’), are
1.943(6), 1.991(6), 1.912(6), 1.865(4) and 2.119(5) Å,
respectively (Table 2); as expected, the bond lengths in 1P are
similar. The coordination geometry of the Mn(III) ion is best
described as distorted square pyramidal, and is consistent with
the presence of a Jahn-Teller distorted d4 species; the MnN
and MnO bond lengths are similar to those commonly
observed for other related Mn(III) complex species.
Results and discussion
Synthesis and structural characterization
Initially, it was envisaged that H3L might be synthesised through
a straight forward two-step procedure involving the formation
of a monoamide of the required diamine by reaction with
phenyl salicylate followed by condensation of this intermediate
with 2-aminobenzaldehyde. This second step, however, proved
to be troublesome due to the tendency of 2-
aminobenzaldehyde to oligomerise,37 and ultimately an in situ
procedure was employed in which Mn(OAc)2·4H2O was added
to the corresponding ligand reaction solution, leading to the
mixed isomeric complexes being isolated as their Mn(III)
derivatives (following aerial oxidation). Since amide ions are too
strong base to exist in a solution, the deprotonation of amino
group may be rationalized to occur after its coordination to the
metal ion.38The dark brown colour of the products suggested
that they were not Mn(II) derivatives. Elemental analyses and
FT-IR spectroscopy indicated the absence of acetate anions and
also that the bound ligands were triply deprotonated, in
keeping with the presence of Mn(III) centres (and as established
previously for related Mn(III) complexes prepared under similar
conditions).36 Final confirmation of the nature of the products
was obtained from their single crystal X-ray structure
determinations.
As briefly mentioned earlier, the selection of different crystals
for X-ray studies enabled the presence of both the right- and
left-handed helices to be identified. For each of the crystal
structures (1M/1P) reported here, the crystal analysed was
found to be enantiomerically pure, with the value of the flack
parameter having a magnitude of less than 0.023 (see Table 1).
The crystals were synthesised by slow evaporation from the
reaction mixture and, after allowing the solvent to evaporate to
dryness in a beaker, yielded needle crystals in ‘colonies’ at the
bottom of the beaker (Figure S2a). The solid-state CD spectra
for single crystals from two colonies were determined using the
KBr pellet technique (Figure S2b). The spectra were found to
exhibit opposite Cotton effects, centred at about 500 nm, in
accord with the formation of enantiomers via spontaneous
resolution during the crystallization process. Clearly, an excess
of either left-handed or right-handed enantiomer crystals
occurred in the respective crystal colonies mentioned above.
Scheme 1. Synthetic pathway to MnL.
[MnL] crystallizes in the lattice space group P212121, indicating
that the crystals are chiral (although the space group itself is
not). The chirality of the crystal is associated with the
conformation of the salen derivative’s central chelate ring
which renders each complex unit chiral (Figure 1a). 1D
polymeric chains run parallel to the a axis and involve
coordination of the amido-O of one complex unit to the Mn(III)
centre in a neighboring unit (Figure 1b). The 1D polymer chain
is helical, with the left-handed (1M) chain incorporating
complex units in which all the central five-membered chelate
rings (Mn1N1C8C9N2) have a  conformation, whereas, all
the corresponding five-membered rings in the right-handed
chain have a  conformation (Figure 2). The lattice for [MnL]
viewed down the a axis (end-on to helical columns of complex
units) is shown in Figure S1. The pitch of the helix is 7.856(1) Å,
Figure 1. (a) Molecular structure of one complex unit in the 1M
coordination polymer chain. The remaining axial coordination
position is filled by an amido oxygen from an adjacent unit. (b)
View of the one-dimensional helical chain for 1M. Hydrogen
atoms are omitted for clarity.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
Dalton Transactions
Please do not adjust margins
Journal Name
ARTICLE
Mn–N3
Mn–O2
1.924(2)
2.124(2)
V1ie.w91A7rt(i5cl)e Online
DOI: 10.1039/C9DT00593E
2.121(5)
Angles
C7–O2–Mn1’
160.9
160.8
Magnetic properties
[Mn(L)] (1)
The temperature dependence of the direct-current (dc)
magnetic susceptibility for the racemic mixture of 1M and 1P
was measured in the range 2.0300 K (Figure 3). At room
temperature, the χmT value of 2.64 cm3 K mol1 is slightly lower
than the expected value for a high-spin Mn(III) ion (3.0 cm3 K
mol1, g = 2). Upon lowering the temperature, the χmT value
decreases continuously and reaches a minimum of 0.357 cm3 K
mol1 at 2.0 K, indicating the presence of antiferromagnetic
intermolecular interactions. The magnetic interactions in the
1M and 1P isomers, with their similar bond length and angles
(Table 2), were assumed to be equal and the experimental data
were fitted based on a linear chain assuming Heisenberg
isotropic coupling according to Fisher’s expression for S = 2.39
Molecular field correction was taken into account the Mean-
Field Approximation as zJ’ for the interpretation of the magnetic
interaction between the chains (eqn (1)(2)).
Figure 2. Mirror image relationship between the helical coordination
polymers 1M and 1P. Hydrogen atoms are omitted for clarity.
Table 1. Crystallographic data for [MnL] (1M and 1P).
Compound
1M
C18H18MnN3O2
363.29
1P
C18H18MnN3O2
363.30
formula
formula weight
crystal system
space group
a / Å
Orthorhombic
P212121
7.8555(9)
11.9365(12)
16.7493(14)
90.0000
90.0000
90.0000
1570.5(3)
4
Orthorhombic
P212121
7.8586(11)
11.9567(13)
16.759(3)
90.0000
90.0000
90.0000
1574.7(3)
4
푁푔2µ2푆(푆 + 1) 1 + 푢
=
(1)

[
]
[
]
3푘
퐽푆(S + 1)
1 ― 푢
푘푇
b / Å
u = coth
―
(푆 = 2)
[
]
[
]
푘푇
퐽푆(푆 + 1)
c / Å
 / º

=
(2)
푀퐹퐴

 / º
1 ― (푧퐽′/푁푔2µ2)

 / º
V / Å3
The fit gave the following values: J = 2.48 cm1, g = 1.96, zJ’= 0.03
cm-1. These interactions are expected to involve dz2 orbital
interactions because the dz2 orbital has been assumed to make the
main contribution to the magnetic coupling in Jahn-Teller distorted
systems.34
Z
T / K
123
123
Dcalc (g cm-1)
1.536
1.532
F000
752.00
752.00
µ(MoK) (cm-1)
reflns collected
unique data
parameters
R1 [I > 2(I)]
wR2 [I > 2(I)]
R1 (all data)
wR2 (all data)
G.O.F.
8.561
8.538
13520
10267
3210
3215
14.46
14.08
0.0278
0.0579
0.0611
0.1077
0.0319
0.901
0.0623
0.1198
1.060
0.997
0.001(11)
1862151
-0.03(3)
1862114
Flack  parameter
CCDC
Table 2 Selected bond Lengths (Å) and angles (º) for 1P/M.
Compound
Bond length
Mn–O1
1M
1P
1.860(2)
1.952(2)
1.989(2)
1.867(4)
1.945(5)
1.989(5)
Mn–N1
Mn–N2
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 4 of 6
ARTICLE
Journal Name
Figure 3. Temperature dependent magnetic susceptibility data [MnL] (1). 1 adopts a helical arrangement, with VsiepwoAnrttiaclne eOonluines
DOI: 10.1039/C9DT00593E
for [Mn(L)]. Plots of mT versus T (▲) measured in a 5000 Oe resolution occurring on crystallization to yield isomeric
applied field. The solid black line represents the best fit. The homochiral left-handed and right-handed helical structures as
coupling interactions modelled are indicated by the red arrows. single crystals despite both isomers being derived from an
achiral free ligand. The temperature-dependent magnetic
Antiferromagnetic coupled 1D Mn(III) coordination polymers susceptibilities of 1 revealed the existence of antiferromagnetic
exhibit the possibility of exhibiting weak ferromagnetism due to interactions (J = 2.7 cm1) occurring via the amido-bridges
spin canting, and several weak ferromagnetic azide-bridged between Mn(III) centers. Further magnetic characterization
systems of salen-based Mn(III) coordination polymers have revealed that 1 behaves as a weak ferromagnet that arises from
been reported.3135 The field dependence of the magnetization the presence of spin canting. It is noted that the respective
was measured in the range -50 kOe to 50 kOe at 2, 5 and 10 K isomers of 1 are homochiral weak ferromagnets arising from
(Figure 4a, Figure S4). At 2 K, the magnetization increases with the spin canting. As such, they represent rare examples of salen-
magnetic field at low magnetic fields, while it increases slowly derivative based, one-dimensional homochiral systems of this
and in an almost linear fashion at high magnetic fields. The type.
magnetization value reaches ca. 0.7 Nβ mol-1 at 50 kOe, which
is far from the expected saturation value of 4.0 Nβ mol-1 (one
MnIII ion, g = 2 and S = 2). A hysteresis loop in the ordered phase
with a relatively large coercive field of 3.0 kOe and a remnant
magnetization of 0.0037 Nβ mol-1 was detected, implying the
existence of canted spins (Figure S5a). The coercive field of 3.0
kOe is about ten times that of the amido-bridged 1D complex
[L4Mn(CH3OH)]n
(L4
=
(E)-2-hydroxy-N-(2-((2-
hydroxybenzylidene)amino)ethyl)benzamide) reported by
Costes and coworkers.36 The M(H) data at 2 K exhibit field-
induced critical fields of around H = 20 kOe, as determined by
the dM/dH plot (Figure S5b). The coercive field is decreased on
increasing the temperature, and the hysteresis loop measured
at above the ordering temperature is completely closed,
indicating the disappearance of the ordered canted spins.
The field-cooled magnetization (FCM) was measured in a field
range of 140 kOe to confirm the spin canting (Figure 4b).
During the cooling process, an abrupt rise in χm at around 7 K
was observed under an applied field of 200 Oe, with this sharp
rise in χm gradually vanishing on increasing the applied field.
Under an applied field of larger than 7000 Oe, no such
remarkable rise was observed and χm decreased from its
maximum observed at 7 K. These behaviors are caused by a spin
arrangement, demonstrating the existence of canted spins. The
canting angle (α) is estimated to be ~1.67 which was calculated
from sin-1 (Mw/Ms), where Mw is the magnetization induced by
a weak magnetic field and Ms is the saturation magnetization.40
The spin canting arises from the presence of two slanted basal
planes incorporating Mn(III) ions with single ion anisotropy.
The zero-field-cooled (ZFC) and field-cooled (FC) magnetization
was measured under an applied field of 5 Oe (Figure 4c). Both
ZFC and FC curves show abrupt increases below 7 K, indicating
the occurrence of spin ordering. The temperature dependence
of the ac magnetic susceptibilities at 1000 Hz (Figure 4d)
exhibits the characteristic peak of an antiferromagnet at TN = 7
K, where the in-phase part χm′ reaches a maximum; the out-of-
phase χm″ reflection was also observed. This is indicative of
long-range magnetic ordering.
Figure 4. (a) M vs H plots at 2.0 K. (b) The χm vs T plots in a field
range of 140 kOe. (c) Zero-field-cooled magnetization (ZFC)
and field-cooled magnetization (FC) curves under an applied
field of 5 Oe. (d) Variable-temperature in-phase (χm) and out-
of-phase (χm) components of the ac susceptibilities at 1000 Hz
collected under zero dc field.
Experimental
Materials and Instruments.
All materials and reagents were commercially available and
used without further purification. Elemental analyses (C, H, N)
were carried out on a J-SCIENCE LAB JM10 analyzer at the
Instrumental Analysis Centre of Kumamoto University. Infrared
(IR) spectra were measured on a Spectrum Two FT-IR
spectrometer (PerkinElmer).
Ligand Syntheses.
The synthesis of H3L and were based on procedures previously
described by us.4142
N-(2-amino-2-methylpropyl)-2-hydroxybenzamide.
Conclusions
Phenyl salicylate (2.14 g, 10 mmol) in 2-propanol (80 mL) was
added dropwise with stirring over 1 h to a 2-propanol solution
In summary, we report here the synthesis and magnetic
properties of the homochiral Mn(III) coordination polymer
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
Dalton Transactions
Please do not adjust margins
Journal Name
ARTICLE
(10 mL) containing 2-methyl-1,2-propanediamine (0.88 g, 10
mmol). The mixture was stirred for 2 days at room temperature.
The resulting white precipitate was collected by filtration,
washed with a small amount of 2-propanol, and dried under
reduced pressure. Yield: 1.47 g (70%). Anal. calc. for C11H16N2O2:
C, 63.44; H, 7.74; N, 13.45; Found: C, 63.46; H, 7.89; N, 13.28 %.
1H NMR (500MHz, DMSO-d6): δ 1.08 (s, 6H, CH3), 3.26 (s, 2H,
CH2), 6.68 (t, 1H, C(5)H), 6.80 (d, 1H, C(3)H), 7.23 (t, 1H, C(4)H),
7.83 (d, 1H, C(6)H), 9.71 (l, 1H, NH). Characteristic IR
absorptions: 3264, 2969, 1620, 1559, 1536 cm1.
References
View Article Online
DOI: 10.1039/C9DT00593E
1
2
3
4
5
6
7
8
9
S. Osa, T. Kido, N. Matsumoto, N. Re, A. Pochaba and J.
Mrozinski, J. Am. Chem. Soc., 2004, 126, 420421.
A. J. Tasiopoulos, A. Vinslava, W. Wernsdorfer, K. A. Abboud,
G. Christou, Angew. Chem. Int. Ed., 2004, 43, 21172121.
W.–X. Zhang, T. Shiga, H. Miyasaka, M. Yamashita. J. Am.
Chem. Soc., 2012, 134, 6908−6911.
E. Coronado, J. R. GalánMascarós, C. MartíGastaldo, J. Am.
Chem. Soc., 2008, 130, 14987–14989.
E. Coronado, J.R. GalánMascarós, C. J. GómezGarcia, V.
Laukhin, Nature. 2000, 408, 447–449.
O. Kahn, Y. Pei, M. Verdaguer, J. P. Renard, J. Sletten, J. Am.
Chem. Soc. 1998, 110, 789792.
S. Ferlay, T. Mallah, R. Ouahès, P. Veillet, M. Verdaguer, Inorg.
Chem., 1999, 38, 229234.
S. M. Humphrey, P. T. Wood, J. Am. Chem. Soc., 2004, 126,
13236–13237.
G. L. J. A. Rikken, E. Raupach. Nature, 1997, 390, 493–494.
[Mn(L)] (1)
A mixture of N-(2-amino-2-methylpropyl)-2-hydroxybenzamide
(0.208 g, 1.00 mmol) and 2-aminobenzaldehyde (0.121 g, 1.00
mmol) in ethanol (40 mL) was stirred for 1 h at 70 °C in air.
Mn(OAc)2·4H2O (0.245 g, 1.00 mmol) in ethanol (10 mL) was
added to the resulting solution and stirring was continued for 2
h at 70 °C (also in air). 1 was obtained as a brown powder which
was recrystallized from methanol to give brown needle crystals.
10 L. D. Barron, Nature, 2000, 405, 895896.
11 N. Hur, S. Park, P. A. Sharma, J. S. Ahn, S. Guha, SW. Cheong,
Nature, 2004, 429, 392395.
12 J. H. Lee, L. Fang, E. Vlahos, X. Ke, Y. W. Jung, L. F. Kourkoutis,
J.W. Kim, P. J. Ryan, T. Heeg, M. Roeckerath, V. Goian, M.
Bernhagen, R. Uecker, P. C. Hammel, K. M. Rabe, S. Kamba, J.
Schubert, J. W. Freeland, D. A. Muller, C. J. Fennie, P. Schiffer,
V. Gopalan, E. JohnstonHalperin, D. G. Schlom, Nature, 2010,
466, 954958.
Yield: 0.159
g
(44%). Anal. calc. for [MnL]·0.5H2O
(C18H18MnN3O2·0.5H2O): C, 58.09; H, 5.15; N, 11.29; Found: C,
58.30; H, 5.28; N, 11.11 %. Characteristic IR absorptions: 3343,
1613, 1597, 1571, 1531 cm1.
13 P. Jain, V. Ramachandran, R. J. Clark, H. D. Zhou, B. H. Toby, N.
S. Dalal, H. W. Kroto, A. K. Cheetham, J. Am. Chem. Soc., 2009,
131, 13625–13627.
14 Crassous. J. Chem. Soc. Rev., 2009, 38, 830845.
15 Q. Zhu, T. Sheng, R. Fu, C. Tan, S. Hu and X. Wu, Chem.
Commun., 2010, 46, 9001–9003.
16 T. Ezuhara, K. Endo and Y. Aoyama, J. Am. Chem. Soc., 1999,
121, 32793283.
17 I. Mihalcea, N. Zill, V. Mereacre, C. E. Anson and A. K. Powell,
Cryst. Growth Des., 2014, 14, 47294734.
18 K. K. Bisht and E. Suresh, J. Am. Chem. Soc., 2013, 135,
1569015693.
19 C. J. Milios, R. Inglis, A. Vinslava, R. Bagai, W. Wernsdorfer, S.
Parsons, S. P. Perlepes, G. Christou, E. K. Brechin, J. Am. Chem.
Soc., 2007, 129, 1250512511.
20 T. C. Stamatatos, D. FoguetAlbiol, S.C. Lee, C. C. Stoumpos,
C. P. Raptopoulou, A. Terzis, W. Wernsdorfer, S. O. Hill, S. P.
Perlepes, G. Christou, J. Am. Chem. Soc. 2007, 129,
94849499.
21 X. Chen, S.–Q. Wu, A.–L. Cui, H.Z. Kou, Chem. Commun.,
2014, 50, 21202122.
22 C. Papatriantafyllopoulou, S. Zartilas, M. J. Manos, C. Pichon,
R. Clėrac, A. J. Tasiopoulos, Chem. Commun., 2014, 50,
1487314876.
23 C.I. Yang, Z.–Z. Zhang, S.–B. Lin, Coord. Chem. Rev., 2015,
289290, 289–314.
24 K. Bernot, J. Luzon, R. Sessoli, A. Vindigni, J. Thion, S. Richeter,
D. Leclercq, J. Larionova, A. v. d. Lee, J. Am. Chem. Soc., 2008,
130, 16191627.
25 B. Cheng, F. Cukiernik, P. H. Fries, J.–C. Marchon, W. R.
Scheidt, Inorg. Chem., 1995, 34, 46274639.
26 T.–T. Wang, M. Ren, S.–S. Bao, B. Liu, L. Pi, Z.–S. Cai, Z.–H. Z.–
H. Zheng, Z.–L. Xu, L.–M. Zheng, Inorg. Chem., 2014, 53,
3117−3125.
27 T.–T. Wang, M. Ren, S.–S. Bao, Z.–S. Cai, B. Liu, Z.–H. Zheng,
Z.–L. Xua, L.–M. Zheng, Dalton Trans., 2015, 44, 42714279.
28 T. Senapati, C. Pichon, R. Ababei, Mathonière, C.; Clérac. R.
Inorg. Chem., 2012, 51, 37963812.
Physical measurements
Single-crystal X-ray diffraction data for both enantiomers of 1
were obtained by selecting single crystals from different
‘colonies’ of crystals formed on crystallization from the reaction
mixture. The data were collected with a Rigaku XtaLAB mini II
diffractometer. The structures were solved by direct methods
(SHELXT43) and refined by full-matrix least-squares refinement
using the SHELXL44 program. Hydrogen atoms were refined
geometrically using a riding model. Crystallographic data and
structural refinements for
1
(both enantiomers) are
summarised in Table 1. Variable-temperature dc magnetic
susceptibility, ac magnetic susceptibility measurements, and
field dependence of magnetization were performed on a
superconducting quantum interference device (SQUID)
magnetometer (Quantum Design MPMS XL). Circular dichroism
(CD) spectra of KBr pellets containing the samples were
measured by a JASCO J-820 spectrophotomer at RT.
Acknowledgements
This work was also supported by KAKENHI Grant-in-Aid for
Scientific Research (A) JP17H01200. This work was supported by
JSPS Grant-in-Aid for Young Scientists (B) JP18K14245, JSPS
Grant-in-Aid for Scientific Research on Innovative Areas
(Dynamical Ordering & Integrated Functions JP16H00777,
Mixed Anion JP17H05485). This work was partially supported by
the Cooperative Research Program of ‘Network Joint Research
Centre for Materials and Devices.
Conflicts of interest
There are no conflicts to declare.
29 C. Yang, Q.–L. Wang, J. Qi, Y. Ma, S.–P. Yan, G.–M. Yang, P.
Cheng, D.–Z. Liao, Inorg. Chem., 2011, 50, 4006–4015.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 6 of 6
ARTICLE
Journal Name
30 M.–X. Yao, Q. Zheng, X.–M. Cai, Y.–Z. Li, Y. Song, J.–L. Zuo,
Inorg. Chem., 2012, 51, 2140−2149.
View Article Online
DOI: 10.1039/C9DT00593E
31 H. H. Ko, J. H. Lim, H. C. Kim, C. S. Hong, Inorg. Chem., 2006,
45, 88478849.
32 M. Yuan, F. Zhao, W. Zhang, Z.–M. Wang, S. Gao, Inorg. Chem.,
2007, 46, 1123511242.
33 J. H. Yoon, J. W. Lee, D. W. Ryu, S. W. Yoon, B. J. Suh, H. C. Kim,
C. S. Hong, Chem. Eur. J., 2011, 17, 3028–3034.
34 K. R. Reddy, M. V. Rajasekharan, J.P. Tuchagues. Inorg.
Chem., 1998, 37, 59785982.
35 J. H. Yoon, D. W. Ryu, H. C. Kim, S. W. Yoon, B. J. Suh, C. S.
Hong, Chem. Eur. J., 2009, 15, 36613665.
36 J.–P. Costes, F. Dahan, B. Donnadieu, M.–J. R. Douton, M.–I. F.
Garcia, A. Bousseksou, J.–P. Tuchagues, Inorg. Chem., 2004,
43, 27362744.
37 L. T. Taylor, S. C. Vergez and D. H. Busch, J. Am. Chem. Soc.,
1966, 88, 31703171.
38 S. Gakias, C. Rix, A. Fowless, M. Hobday, Inorg. Chem. Acta,
2006, 359, 2291-2295.
39 M. E. Fisher, Am. J. Phys., 1964, 32, 343.
40 Kahn, O. Molecular Magnetism; VCH: Weinheim, Germany,
1993.
41 S. Kusumoto, F. Kobayashi, R. Ohtani, Y. Zhang, J. Harrowfield,
Y. Kim, S. Hayami. M. Nakamura, Dalton Trans., 2018, 47,
95759578.
42 F. Kobayashi, R. Ohtani, S. Teraoka, W. Kosaka, H. Miyasaka,
Y. Zhang, L. F. Lindoy, S. Hayami, M. Nakamura, Dalton Trans.,
2017, 46, 8555–8561.
43 G. M. Sheldrick, SHELXT – Integrated Space-Group and
Crystal-Structure Determination. Acta Crystallogr, Sect. A
2015, 71, 3–8.
44 G. M. Sheldrick, Crystal Structure Refinement with SHELXL.
Acta Crystallogr Sect. C 2015, 71, 3–8.
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins