Newly designed Mn (III)–W(V) bimetallic assembly built by manganese (III) Schiff–base and octacyanotungstate(V) building blocks: Structural topologies, and magnetic features

Article abstract of DOI:10.1002/aoc.5914

New complex [Mn (SB)₂(DMF)₂] [W (CN)₈] hereafter referred to as complex 1, which was prepared by self–assembly of [Mn (SB)₂(DMF)₂]³⁺ and [W (CN)₈]^3? and structurally c

Full text of DOI:10.1002/aoc.5914

Received: 6 April 2020
DOI: 10.1002/aoc.5914
Revised: 7 June 2020
Accepted: 11 June 2020
F U L L P A P E R
Newly designed Mn (III)–W(V) bimetallic assembly built
by manganese (III) Schiff–base and octacyanotungstate(V)
building blocks: Structural topologies, and
magnetic features
Mohd. Muddassir1
| Abdullah Alarifi1 | Mohd Afzal1 | Nayim Sepay2
1Catalytic Chemistry Research Chair,
Department of Chemistry, College of
Science, King Saud University, Riyadh,
11451, Saudi Arabia
2Department of Chemistry, Jadavpur
University, Kolkata, 700032, India
New complex [Mn (SB)2(DMF)2] [W (CN)8] hereafter referred to as complex
1, which was prepared by self–assembly of [Mn (SB)2(DMF)2]3+ and
[W (CN)8]3− and structurally characterized by elemental analysis, infrared
(IR) and single crystal X–ray techniques (H2SB is Schiff base derived from
the condensation of salicylaldehyde and N,N–diethylethylenediamine and
DMF is dimethylformamide). The structure consists of 1–D supramolecular
chains and further stacks to give a 3–D supramolecular architecture whose
Correspondence
Mohd. Muddassir, Catalytic Chemistry
Research Chair, Department of
Chemistry, College of Science, King Saud
University, Riyadh 11451, Saudi Arabia.
Email: mmohammadarshad@ksu.edu.sa;
muddassirchem@gmail.com
molecular fragments are linked by hydrogen bond as well as C − Hꢀꢀꢀπ inter-
actions between [Mn (SB)2(DMF)2]3+ and [W (CN)8]3−. An underlying net
for the representation consists of two types of fragments with 1,4 M5–1 and
1,8 M9–1 topologies and further illustration of the molecular network in
terms of a graph−theory approach using simplification procedure resulted in
the underlying net of 2C1topological type in the complex 1. Magnetic sus-
ceptibility measurements of complex 1 was carried out in the temperature
range 2–300 K, indicates the presence of either magnetic anisotropy zero
field splitting, the effect of intramolecular interactions, or both. Complex
1 follows the Curie–Weiss law with Curie constant value of 3.43 cm3mol−1K,
and the slight negative Weiss constant (−0.60 K) value indicates the predom-
inant antiferromagnetic magnetic exchange interactions.
Funding information
Deanship of Scientific Research, King
Saud University, Grant/Award Number:
RG-1440-076
The magnetic properties of Title complex was investigated thoroughly and
showed that ferromagnetic interaction between W(V) and Mn (III) operate via
the intramolecular H–bonding interaction between cyanide nitrogens and a
hydrogen atom.
K E Y W O R D S
H-bonding; magnetism, Octacyanotungstate(V), Schiff base, X-ray crystallography
1 | INTRODUCTION
same molecular unit, as the magnetic interaction
between these spin carriers can be easily controlled to
In the past few decades, considerable efforts have been
given to create new molecule–based magnets via a combi-
nation of dissimilar paramagnetic metal ions within the
obtain materials with desired properties.[1–13] A lot of
large and ultra–large complexes with controlled nuclea-
rity based on d– and f–metal centers have been
Appl Organomet Chem. 2020;e5914.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5914

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MUDDASSIR ET AL.
synthesized as SMMs. One such example is a family of het-
erometallic architecture containing polycyanometallates
of Mo(V), Nb(V), or W(V),[14] which have been employed
to synthesize cyano–bridged magnetic complexes with
fascinating magnetic properties, such as the TC's
magnets,[15–18] single–molecule magnets (SMMs),[19–25]
and single chain magnets SCMs).[26–28] Besides, these
building components materialize well appropriate to
obtain low dimensional architectures such as chains.[29–32]
Our interest in this field concerns the heterometallic archi-
tectures that behaves as magnet at low temperatures; in
other words, their field–induced magnetization relaxes
slowly, even upon removal of the applied direct current
(dc) field.
bridging and chelate bridging resulting in exciting
magnetic property.[49] Ashutosh Ghosh et al.;[50] has
reported two Mn (III) complexes by using Schiff base
with sodium azide exhibiting interesting magnetic
properties. Inspired from his results and being moti-
vated from our previous studies of octacyanometallate–
based magnets, we construct magnetic materials by
replacing the sodium azide with W (CN)8 ions since
this may improve the magnetic properties because W
(CN)8 can mediate magnetic exchange interaction as it
can adopt three different spatial configurations
(e.g., square antiprism (D4h), dodecahedron (D2d), and
bicapped trigonal prism (C2V) depending on their
chemical environment [32]. More importantly, these
Many molecules are displaying SMM property, but
the majority of them being Mn (III) complexes. This is
because Mn (III) complexes often show relatively large
ground state S values, as well as relatively large (and
negative) D values associated with the presence of
Jahn–Teller, distorted Mn (III) atoms. The complexes
self–assembled by Mn (III)–(Schiff bases) are always of
great interest because of the above–said reason. Thus
far, many relevant magnetic complexes, including some
SMMs and SCMs, have been reported.[19,20,33–41] Some
results have been reported in which Mn (III)–Schiff
bases act as the precursors in cyanide–bridged com-
plexes. The position and size of the substituted groups
on the Schiff base ligands have been revealed to play
an essential role in determining the structure of
resulting complexes.[42,43] These findings have triggered
the investigation of new molecular complexes based on
manganese metal ions. However, compared with solely
3d (mainly Mn (III))–based magnetic systems, magnetic
assemblies with enhanced exchange couplings and
anisotropic properties can be constructed with heter-
ometallic 4d/5d metal ions, because they possess more
radially extended orbitals and exhibit greater spin
−orbit coupling. They can build a wide variety of
molecular architectures from 0D to 3D depending on
the coordination versatility to 3d transition metal ions
in self–assembly.[36,44–46] Cyano–bridged metal assem-
blies based on octacyanometalates [M (IV)/(V).
(CN)8]4−/3– (M = Mo, W and Nb)[47,48] have drawn
particular attention in the design and synthesis of the
new molecule–based magnets because the cyanide
bridge can mediate strong coupling interactions
between the metal ions.
complexes lead to a significant increase of the
exchange interactions with respect to 3d ions
cyanometallates, and also an enhanced exchange inter-
action may be expected due to the increased overlap
between the diffuse orbitals of octacyanotugstate with
Mn (III) metal ion.[51–53] All of these merits make
octacyanotungstate a promising candidate in compari-
son to diamagnetic sodium azide. As part of our effort
in this direction, herein, we describe the syntheses,
characterization, and magnetic properties of self–
assembly of octacyanotungstate with Mn (III)–(SB),
which proceeds to give 1–D arrangement of the build-
ing blocks employed.
2 | EXPERIMENTAL SECTION
2.1 | Physical measurements
The IR spectra were recorded with a VECTOR 22 spec-
trometer using KBr pellets in the 200–4,000 cm−1 region.
Elemental analyses of C, H and N were performed on a
PerkinElmer 240C elemental analyzer. TGA/DSC was
performed on Universal V3.8 B TA SDT Q600 Build
51 thermal analyzer under a nitrogen atmosphere using
alumina powder as the reference material. The data of
magnetic properties for crystalline samples were collected
on a Quantum Design MPMP–XL 7 superconducting
quantum interference device (SQUID) magnetometer.
Corrections of magnetic susceptibilities were carried out
considering both the sample holder as the background
and the diamagnetism of the constituent atoms estimated
from Pascal's constant.
From a synthetic and magnetic point of view,
Schiff–base ligands is a good choice to develop enticing
metal complexes because it contains multidentate
donor atoms and can coordinate to many metal cen-
ters and also the phenolic group can display a variety
of bonding geometries such as monodentate, bidentate,
2.2 | Starting materials
Chemicals and solvents were purchased from commercial
sources as analytical reagents and used without further

MUDDASSIR ET AL.
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TABLE 1 Crystal structural data and refinement parameters
for complex 1
purification. [HN(n–C4H9)3]3W(CN)8.2H2O was prepared
according to the literatures procedure.[54]
Caution! Cyanides are hyper–toxic and hazardous,
thus, should be handled in small quantities and with
great caution!
CCDC No
1,977,017
Formula
C40H54MnN14O4W
1033.76
Formula weight
Temperature/K
Crystal system
Space group
293(2)
2.2.1 | Synthesis
triclinic
P − 1
The unprotonated Schiff base ligand (H2SB) was pre-
pared by refluxing salicylaldehyde (0.1 ml, 1 mmol)
with N,N–Diethylethylenediamine (0.116 ml, 1 mmol)
in methanol (10 ml) for 30 min. The resulting dark
yellow solutions of Schiff base ligand was subsequently
used for complex formation.
a/Å
10.4518 (12) Å
12.8571 (15) Å
17.325 (2) Å
78.931 (2)ꢁ
89.489 (2)ꢁ
81.742 (2)ꢁ
2260.7 (5)
b/Å
c/Å
α/ ꢁ
β/ ꢁ
γ/ ꢁ
Volume/Å3
2.2.2 | Synthesis of complex 1
Z
2
ρcalc/mg mm−3
μ/mm−1
1.519
At room temperature, 0.1 mmol of methanolic solution
of Schiff base ligand (2 ml) was added to a 3 ml
methanolic solution of Mn (OAc)2ꢀ4H2O (0.0245 g,
0.1 mmol) followed by a methanolic solution (2 ml) of
[HN(n–C4H9)3]3W(CN)8.2H2O (0.0329 g, 0.033 mmol).
The solution turned brown, and precipitation occurs.
The brown precipitate was dissolved using ca. 2 ml of
DMF. The mixture was kept unstirred in a refrigerator.
The red-colored, X–ray quality, prismatic shaped single
crystals started to separate within a few hours and were
collected after two days. Yield 28%. Elemental analysis
for C40H54MnN14O4W: C 46.48, H 5.27, N 18.97%; found:
C 46.23, H 5.18, N 18.93%.
2.877
F(000)
1,046
Crystal size/mm3
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness−of−fit on F2
Final R indexes [I > =2σ (I)]
Final R indexes [all data]
Largest diff. Peak/hole/e Å−3
0.25 × 0.22 × 0.2
14,886
10,142 [R (int) = 0.0308]
10,142/0/552
0.985
R1 = 0.0425, wR2 = 0.0940
R1 = 0.0586, wR2 = 0.1015
1.93/−2.18
aR1 = (Σ||Fo| − |Fc||)/Σ|Fo|. bwR2 = [Σ[w (Fo2 − Fc ) ]/Σ[w
2 2
(Fo2)2]]1/2, where w = 1/[σ2(Fo2) + (αP)2 + bP].
2.3 | X–ray structure determination
acetate followed by the reaction with [HN(n–C4H9)3]3
W(CN)8.2H2O in methanol/DMF under ambient condi-
tions as red crystalline solids within a few hours,
containing all coordinately isolated molecules on
keeping the solutions in a refrigerator as shown in
Scheme 1. Regardless of reaction ratios of Mn
(SB) and [HN(n–C4H9)3]3W(CN)8.2H2O the same coor-
dinately isolated molecule was always obtained. On
reaction with Schiff base ligand, Mn (II) was readily
oxidized in the air to Mn (III) and stabilized by com-
plex formation. The complex is stable towards air and
moisture. As per our expectation, the applied synthetic
strategy to the formation of complex 1 by introducing
the steric hindrance at Schiff base ligand may
prevented the formation of cyano-bridged complex.
Since the [Mn (SB)2(DMF)2]3+ and [W (CN)8]3− are
isolated, attempts to connect through cyanide–bridged
by changing solvents, different organic bases such as
X-Ray crystal structure determination has been given in
supporting information in detail. Details of the crystallo-
graphic data collection, structural determination, and
refinement are summarized in Table 1. Selected bond dis-
tances and angles are listed in Table S1. Data can also be
obtained free of charge in cif format by request from The
Cambridge Crystallographic Data Centre at www.ccdc.
cam.ac.uk/data_request/cif.
3 | RESULTS AND DISCUSSION
3.1 | Synthetic strategy
The new MnIII complex (complex 1) has been prepared
with the tridentate Schiff base (SB) ligands (which
in our case act as bidentate) with manganese (II)

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MUDDASSIR ET AL.
SCHEME 1 Synthetic route for complex 1
NEt3, NMe4OH, NaOH and also by increasing the time
duration/temperature of the reaction mixture, but all
of our efforts were unsuccessful and led to the same
product, as established by means of initial cell check
of X–ray diffraction and IR. In a similar report, Hong,
et al. synthesized a unique isolated W(V)–Mn (III)
bimetallic compounds using different Schiff–base in
acetonitrile but a similar method, which indicates the
feasibility of the synthetic procedure.[55] We also mea-
sured the TGA and its data revealed that one of the
DMF solvent molecules (calcd 6.7%) is lost before
complex 1 begins to decompose at around 180 ꢁC
(Figure S1) consistent with other previously reported
W(V)-based complexes.[56]
Both Mn (III) metal atoms occupy a distorted octahe-
dral coordination sphere (Figure S2a) coordinated to the
one molecule of SB ligand, one molecule of DMF, and
the other half set of Schiff base ligand and DMF molecule
were generated through a center of symmetry. In case of
Mn1 coordination sphere being equatorially coordinated
to the Schiff base ligand through N9, O1, and axially
coordinated to DMF O2, similarly in case of Mn2, the
coordination through Schiff base ligand is N12, O3 and
DMF are O4. Around Mn1 and Mn2, all similar atoms
are attached in a trans− configuration. The W(V) center
have
a
square antiprism molecular geometry
(Figure S2b). The bond length and angles are nearly the
same in both Mn (III) centers. The Mn − ODMF = 2.242(4) Å
and Mn − Oph = 1.867(3) Å bond distances are similar in
both the Mn (III) metal centers, all being common coor-
dination bonds as reported by a similar type of Mn (III)
complexes, [50] whereas the only difference is the distance
of imine nitrogen. In the case of Mn1 the Mn − Nimine
bond distance is 2.052(4) Å, while in the latter case, it
was found to be 2.061(4) Å heterometallic are in the nor-
mal range (Table S1). The oxidation states of Mn (III)
metal ions were deduced from the metric parameters and
charge balance consideration, which was further con-
firmed by bond valence sum (BVS) calculations (Table 2).
3.2 | Structure description
The asymmetric unit of complex 1 is shown in Figure 1a
and the unit cell packing of the self−assembled molecular
framework inside the crystal is given in Figure 1b. The
crystallographic data collection and structural refinement
are listed in Table 1, while, bond distances and bond
angles are given in Table S1. The single X − ray diffraction
analyses revealed that complex 1 includes two different
metal atoms {Mn (III) and W(V)} (Figure 1a). In the
[Mn (SB)2(DMF)2]3+ part, the two aromatic rings and the
metal ion are almost coplanar and the oxygen atoms of
both the SB stay outside of the plane with C2 symmetry.
The space group is P − 1 and the unit cell packing of the
self−assembled [W (CN)8]3− and [Mn (SB)2(DMF)2]3+
inside the crystal is shown in Figure 1b.
TABLE 2 BVS calculations for complex 1
[Mn (SB)2(DMF)2]
[W (CN)8]
Mn2+
Mn3+
Mn4+
Mn1
3.2245662 3.0111414 3.0610468
3.1967996 2.9842608 3.0352342
Mn2
FIGURE 1 (a) Crystal
structure of complex 1.
(b) Packing of the self
−assembled [W (CN)8]3− and
[Mn (SB)2(DMF)2]3+ inside the
crystal (H − atoms omitted
for clarity)

MUDDASSIR ET AL.
5 of 10
The assignment of both Mn (III) centers based on bond
distances is in line with the BVS values. The overall
coordination geometry around Mn (III) may, therefore,
be described as an elongated octahedron, which is
expected from the Jahn–Teller distortion. The four donor
atoms in the equatorial plane O1, N9, O1i and N9i
(in case of Mn1) and O3, N12, O3i and N12i (in case of
Mn2) are in the same plane and both Mn (III) atoms are
almost planar from this plane. The phenyl rings are
coplanar to each other in each Mn (III) center. Moreover,
the equatorial O1—Mn1—N9 bond angle involving the
Oph and Nimine groups [90.51 (15)ꢁ], while in case of O3—
Mn2—N12 [89.98 (15)ꢁ] is nearly equal to the angle of an
ideal octahedron (90ꢁ), whereas the other equatorial
N9—Mn1—O2 bond angle involving ODMF and Nimine
groups [88.96 (14)ꢁ], and N12—Mn2—O4 [92.72 (15)ꢁ] is
slightly deviated from perfect octahedron (Table S1).
available CN− groups and stabilizes the crystal structures
(Figure 2b). It is worth nothing to mention that the
improper dihedral angles of the two methyl groups of
−NHEt2 are 100.890 instead of zero (Figure S4). This con-
formational preference at 100.890 allows both carbons of
each the ethyl groups to form C − Hꢀꢀꢀπ interactions with
different CN− nitrogen atoms. In this way, one
[W (CN)8]3− unit can interact with alkyl chains of five
different Mn (SB) units (Figure 2b) and able to stabilize
the three–dimensional framework of their 1 − D molecu-
lar assembly. The geometry of W(V) metal ion deserves
particular attention because W (CN)8 polyhedron has a
significant incidence on the strengths of the exchange
interaction.[57]
The geometry of W(V) center surrounded by eight C
atoms from the CN− groups has been analyzed with the
SHAPE program,[58] revealing a distorted square anti-
prism (SAPR−8), the results being tabulated in Table S2.
N1N2N3N4 and N5N6N7N8 comprise the two square
basic planes of the antiprism with the mean deviations of
0.144, and 0.256 Å from each plane, respectively, and
their dihedral angle is 1.6ꢁ. The distances of W(V) to the
N1N2N3N4 plane center and N5N6N7N8 plane center
are 1.754(4) and 1.785(3) Å, resulting in the difference
Δd = 0.031 Å, whereas the related Δd for [W (CN)8]3− is
0.418 Å (Figure 3).
Self−assembly
of
[W
(CN)8]3−
and
[Mn (SB)2(DMF)2]3+ form 1 − D chain whose molecular
fragments are linked by hydrogen bonds between cyanide
nitrogen and a hydrogen atom, which is connected with
positively charged quaternary nitrogen (Figure 2a). Inter-
estingly, the two adjacent [Mn (SB)2(DMF)2]3+ units are
neither parallel nor perpendicular to each other at an
angle 67.200 between two such [MnDMF (SB)] units
(Figure S3). The one–dimensional chain of Mn (III) units
can elongate infinitely along the unit cell axis b. The
67.200 tilting situation of the Mn (III) part allows more
moiety to interact with CN− groups. The alkyl chains
attached to the SB and CN− group of [W (CN)8]3− plays a
prominent key role in the assembling process. Besides,
the 3D supramolecular architecture of complex 1 was
generated, which exhibits strong C − Hꢀꢀꢀπ interactions
between alkyl and imine hydrogens of SB moieties and
The W − C bond lengths range from 2.149(6) to
2.183(5) Å, and the C ≡ N bond lengths from 1.124(7) to
1.144(7) Å. The W − C ≡ N linkages are almost linear, with
the angles ranging from 177.0 (6) to 179.4 (6)ꢁ. All bond
lengths and angles in [W (CN)8]3− in the complex 1 are
comparable with those in reported kinds of litera-
ture.[47,59,60] The Mn − Mn separation within the complex
is 10.077(11) Å, while the distance between each Mn1 − W1
FIGURE 2 (a) 1D chain
of complex 1 along
b − direction. (b) 3D packing of
[Mn (SB)2(DMF)2]3+ and
[W (CN)8]3− inside the unit cell
and hydrogen bonding as well
as C − H … π interactions (H–
atoms omitted for clarity)

6 of 10
MUDDASSIR ET AL.
FIGURE 4 The standard representation of the H − bonded
molecular MOFs in the complex 1. The underlying net of 2C1
topological type obtained after secondary simplification. Red and
yellow spheres correspond to [Mn (SB)2(DMF)2]3+ and
[W (CN)8]3−, respectively
FIGURE 3 The square antiprism geometry of W(V) center
and Mn2 − W2 is 7.482(13) Å and 8.406(8) Å, respectively,
whereas the bond angle is 78.49(3)ꢁ. It is worth noting that
the intermolecular distance could be a major influencing
factor of the magnetic properties in these complexes.
Each subnet of this net contains information about
the spatial arrangement of strong intermolecular con-
tacts, assuming the Ωi is proportional to the strength of
intermolecular interaction (Table S3).
The topological analysis for complex
1
was
performed with the ToposPro program which is the
keystone of the topological analysis for structure
representation and the TTD collection of periodic net-
work topologies.[61,62] The universal approach to the
crystal structure description is to consider all atoms,
and all (even weakest) links between them, which
corresponds to the complete representation, any other
representation with a derived topology is partial. The
topology of a partial representation is described by an
underlying net in the so−called standard representation
of the valence−bonded MOFs.[63,64] The structural
building units for complex 1 showing an underlying net
for the description consists of two types of fragments
with 1,4 M5–1 and 1,8 M9–1 topological type whose
nodes correspond to all metal atoms and the centers of
mass of the organic ligands in the representation of the
underlying net (Figure S5). The standard topological
representation of complex 1 can be described as a chain
of an underlying net of 2C1 topological type whose
nodes correspond to [Mn (SB)2(DMF)2]3+ and
[W (CN)8]3−, respectively in a self–assembled molecular
framework (Figure 4).
In order to further execute the multilevel topolog-
ical explanation [65] of the molecular packing, we
select the value of molecular solid angle (Ωi) as a
criterion, which will serve as a weight factor to be
proportional to the strength of the intermolecular
contact. Using the subroutine generate representations
implemented in ToposPro, different subnets (impor-
tant building blocks of the internet topology) can be
obtained from the underlying net of 2C1 topological
type that contains the edges of weight no less than
a specified value (Figure 5).
3.3 | FT–IR Spectrum
In the spectra of the free salicylaldehyde ligands, the
intense bands stemming from the stretching and bend-
ing vibrational modes of the phenolic −OH around
3,200 cm−1 and 1,410 cm−1, respectively, disappear
from the spectra of the complex 1 indicating the ligand
deprotonation.[66] Also, the bands originating from the
C
−
O
stretching vibrations were observed at
1243–1295 cm−1 in the complex 1. The band at
3400 cm−1 has been assigned to the −NH stretching
vibration of the complex,[67] and its broad feature is
attributed to the formation of hydrogen bonding as
reported in literature by similar complexes[55] while
the bending mode of N − H is present at 1547 cm−1
.
Ghosh et al.;[50] has also reported similar band but
shorter wavelength than title complex probably
because absence of hydrogen bonding. The band at
ꢂ1,611 cm−1 attributable to the ν(−CH=N) of the
Schiff base ligand, coordinated to Mn center. The
stretching frequencies of the −C=O bonds are located
at 1643 cm−1 which are related to the coordinated
DMF molecule.[68] The medium to low intensity bands
at 640 and 444 cm−1 are attributed to the coordination
bonds (Mn − O and Mn − N, respectively) according
to the literature[69] The [W (CN)8]3− based characteris-
tic CN bands in the IR data occur at 2155sh and
2,138 cm−1 for complex 1. The broad absorptions are
centered around 3,400 indicates that hydrogen bonds
are involved in the complex.

MUDDASSIR ET AL.
7 of 10
FIGURE 5 Subnets of the initial net corresponding to the molecular packing in structure at different levels: 2 − c 2C1 ! 4 − c
sql ! 6 − c pcu ! 8 − c hex! 7,18,18 − c net
3.4 | Magnetic properties
2.50 cm3ꢀKꢀmol−1. This nature of the χMT plot sug-
gests a weak antiferromagnetic coupling between para-
magnetic Mn (III) and W(V) centers through H–
bonding. The faster decrease in a low-temperature
region denotes the presence of magnetic anisotropy
zero-field splitting (quite remarkable in Mn (III) cen-
ters), the effect of intramolecular interactions, or
both,[70] but, the contribution of weak antiferromag-
netic interactions cannot be ruled out.
Variable–temperature dc magnetic susceptibility data
for complex 1 was collected in the temperature range
2–300 K under an applied field of 2000 Oe. The χΜT
versus T data, where χΜ is the molar magnetic suscep-
tibility and T is the absolute temperature, is shown in
Figure 6a. The observed χΜT value at 300 K of
3.412 cm3ꢀKꢀmol−1 for 1 is slightly higher to the
expected value of 3.375 cm3ꢀKꢀmol−1 for
a
non–
The magnetic data of complex 1 obey the Curie–Weiss
law [(χΜ = C/(T – θ))] very well, where C and θ
are Curie and Weiss constants, respectively affording
C = 3.43 cm3mol−1K and θ = −0.60 K (Figure 6b).
The Curie constant is in good agreement with the
expected value of 3.375 cm3mol−1K. The overall shape
of the χΜT versus T curve of the 1.8–300 K region and
interacted spin system of two–half Mn (III) ion (S = 2,
C = 3 cm3ꢀKꢀmol−1 with g = 2) and one W(V) ion
(S = ½, C = 0.375 cm3ꢀKꢀmol−1 with g = 2). The mag-
netic data show that χΜT remains almost constant up
to 90 K. Below the cusp temperature, the χΜT product
drastically drops and reach
a
minimum of
FIGURE 6 (a) Temperature dependence of the χΜT product under an applied field of 2000 Oe. (b) Plot of χM−1 vs T for complex 1 at
2000 Oe applied field with the linear fit shown as a red line

8 of 10
MUDDASSIR ET AL.
the negative Weiss constant value indicates the pre-
dominant antiferromagnetic magnetic exchange interac-
tions. This manifests that the isolated metal centers
are antiferromagnetically correlated through the hydro-
gen bonds.
To gain more insight into the magnetic behavior at
low temperatures, field cooled (FC) magnetic suscepti-
bility measurements (Figure S6) were performed from
2–300 K under 2000 Oe applied field. Below 20 K, the
FC magnetization curve shows a gradual increase and
changes its slope further at 9.0 K and shows no satu-
ration effect until the lowest measured temperature.
This shows the presence of an uncompensated spin
below this temperature, which contributes to this net
magnetization.
Efforts to construct other fascinating structures by
reacting to the current Schiff base ligand (SB) and
other less hindered Schiff bases with other transition
metal salts, as well as other rare-earth (III), salts
together with octacyanometallates are continuing in
our laboratory.
ACKNOWLEDGEMENTS
The authors would like to extend their sincere apprecia-
tion to the Deanship of Scientific Research at King Saud
University for funding this work through research group
project number RG–1440–076.
CONFLICT OF INTEREST
The dynamic magnetic properties of complex 1 were
further probed by alternating–current (ac) measurements
in the temperature range 1.9–7 K, as shown in Figure S7.
Under a zero dc field and a 5 Oe ac field oscillating at fre-
quencies between 1 and 1,500 Hz, no ac signal was
observed. However, when a static dc field (2,500 Oe) was
applied, complex 1 displayed a frequency-independent in–
phase (χ’) and frequency-dependent out–of–phase (χ”) sig-
nal, and signal presents two peaks or a peak and a shoul-
der (in case of χ”) at frequencies above than 1,000 Hz at
1.9 K, indicates weak magnetic coupling or possibly the
slow relaxation of magnetization.
The author declares no conflict of interest.
ORCID
Mohd. Muddassir https://orcid.org/0000-0001-7069-
2557
Nayim Sepay https://orcid.org/0000-0001-7702-3989
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How to cite this article: Muddassir M, Alarifi A,
Afzal M, Sepay N. Newly designed Mn (III)–W(V)
bimetallic assembly built by manganese (III)
Schiff–base and octacyanotungstate(V) building
blocks: Structural topologies, and magnetic
features. Appl Organomet Chem. 2020;e5914.
https://doi.org/10.1002/aoc.5914
SUPPORTING INFORMATION
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in the Supporting Information section at the end of this
article.