Single-Molecule Magnetic, Catalytic and Photoluminescence Properties of Heterometallic 3d–4f [Ln{PZn2W10O38(H2O)2}2]11? Tungstophosphate Nanoclusters

Article abstract of DOI:10.1002/ejic.202100528

A series of eleven lanthanide containing di-Zinc (II) substituted heterometallic 3d–4f sandwich-type tungstophosphate nanoclusters [Ln{PZn₂W₁₀O₃₈(H₂O)₂}₂]^11? (Ln=Nd^III, Sm^III, Eu^III, Gd^III, Tb^III, Dy^III, Ho^III, Er^III, Tm^III, Yb^III, and Lu^III) have been synthesized by a single step reaction procedure. These clusters were characterized by various analytical techniques such as single crystal X-ray diffraction (SC-XRD), fourier transform infrared (FT-IR) spectroscopy, high-resolution electro-spray ionization mass spectrometry (HR-ESI-MS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), solid UV/Vis, photoluminescence spectroscopy, powder X-ray diffraction (P-XRD) and thermogravimetric analysis (TGA). All the polyanions are isostructural and consists of a lanthanide ion sandwiched between two units of (1,5) isomer of di-Zn substituted α-Keggin type tungstophosphate. The complexes Sm-2 a, Eu-3 a, Tb-5 a, and Dy-6 a show good photoluminescence behavior. The catalytic properties were examined for the oxidation of thioethers. The catalyst is stable with a high turn over frequency (TOF) of 6250 h^?1 and can be recovered even after 5 consecutive cycles. Furthermore, magnetic properties revealed that Gd-4 a, Tb-5 a, Dy-6 a, Er-8 a, and Yb-10 a show single-molecule magnetic properties.

Full text of DOI:10.1002/ejic.202100528

European Journal of Inorganic Chemistry
Accepted Article
Title: Single-Molecule Magnetic, Catalytic and
Photoluminescence Properties of Heterometallic 3d-4f
[Ln{PZn2W10O38(H2O)2}2]11− Tungstophosphate Nanoclusters
Authors: Vivek Das, Imran Khan, Firasat Hussain, Masahiro Sadakane,
Nao Tsunoji, Katsuya Ichihashi, Chisato Kato, Katsuya Inoue,
and Sadafumi Nishihara
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.202100528
Link to VoR: https://doi.org/10.1002/ejic.202100528
01/2020

10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
Single-Molecule Magnetic, Catalytic and Photoluminescence
Properties of Heterometallic 3d-4f [Ln{PZn2W10O38(H2O)2}2]11−
Tungstophosphate Nanoclusters
Vivek Das,[a] Imran Khan,[a] Firasat Hussain,*[a] Masahiro Sadakane,[b] Nao Tsunoji,[b] Katsuya
Ichihashi,[c] Chisato Kato,[c] Katsuya Inoue,[c,d] and Sadafumi Nishihara*[c,d,e]
Dedication ((optional))
[a]
Mr. Vivek Das, Mr. Imran Khan, Dr. Firasat Hussain
Department of Chemistry
University of Delhi
Faculty of Science, North Campus, Delhi-110007, India
E-mail: fhussain@chemistry.du.ac.in
Homepage URL: http://people.du.ac.in/~firasat/
Prof. Masahiro Sadakane, Dr. Nao Tsunoji
Department of Applied Chemistry
Graduate School of Advanced Science and Engineering, Hiroshima University
1-4-1 Kagamiyama, 732-8527, Higashi-Hiroshima, Japan
E-mail: sadakane09@hiroshima-u.ac.jp
Mr. Katsuya Ichihashi, Chisato Kato, Prof. Katsuya Inoue, Prof. Sadafumi Nishihara
Department of Chemistry
[b]
[c]
Graduate School of Science, Hiroshima University
1-3-1 Kagamiyama, Higashi-Hiroshima, 739-8526, Japan
E-mail: kxi@hiroshima-u.ac.jp, snishi@hiroshima-u.ac.jp
Prof. Katsuya Inoue, Prof. Sadafumi Nishihara
Chirality Research Center (CResCent) and Institute for Advanced Materials Research
Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, 739-8526, Japan
E-mail: kxi@hiroshima-u.ac.jp, snishi@hiroshima-u.ac.jp
Prof. Sadafumi Nishihara
[d]
[e]
JST, PRESTO, 4-1-8, Honcho, Kawaguchi, Saitama, 332-0012, Japan
E-mail: snishi@hiroshima-u.ac.jp
Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate))
Abstract: A series of eleven lanthanide containing di-Zinc (II) Introduction
substituted heterometallic 3d-4f sandwich-type tungstophosphate
nanoclusters [Ln{PZn2W10O38(H2O)2}2]11– (Ln = NdIII, SmIII, EuIII, GdIII,
Polyoxometalates (POMs) are self-assembly of early transition
metal-oxide nanoclusters synthesized under acidic medium which
possesses diverse structural variety along with various
TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII) have been synthesized by a
single step reaction procedure. These clusters were characterized by
various analytical techniques such as single crystal X-ray diffraction
(SC-XRD), fourier transform infrared (FT-IR) spectroscopy, high-
resolution electro-spray ionization mass spectrometry (HR-ESI-MS),
inductively coupled plasma atomic emission spectroscopy (ICP-AES),
solid UV/Vis, photoluminescence spectroscopy, powder X-ray
diffraction (P-XRD) and thermogravimetric analysis (TGA). All the
polyanions are isostructural and consists of a lanthanide ion
sandwiched between two units of (1,5) isomer of di-Zn substituted α-
Keggin type tungstophosphate. The complexes Sm-2a, Eu-3a, Tb-5a,
and Dy-6a show good photoluminescence behavior. The catalytic
properties were examined for the oxidation of thioethers. The catalyst
is stable with a high turn over frequency (TOF) of 6250 h−1 and can be
recovered even after 5 consecutive cycles. Furthermore, magnetic
properties revealed that Gd-4a, Tb-5a, Dy-6a, Er-8a, and Yb-10a
show single-molecule magnetic properties.
a
applications.1a POMs are gaining popularity among the
researchers nowadays due to their wide-scale applications in the
field of magnetism, catalysis, medicine, imaging technique, and
nanomaterial design.1b-1l Usually, polyanions are in plenary form
at lower pH, however at a higher pH, lacunary polyanions are
formed due to the hydrolytic cleavage of W-O-W bridging bonds.
These lacunary POMs are more reactive than the parent
polyanions as they can interact with transition metals as well as
lanthanide cations to form an intriguing variety of architecture
exhibiting versatile topologies. Among them, the Keggin anion
with the formula {XM12O40}, where X is the central hetero atom (X
= SiIV, GeIV, or PV etc.) and M is a transition metal in their high
oxidation state (M = MoVI or WVI etc.), generally form more stable
lacunary species with different isomeric structures. In the past
decades, a vast variety of transition metal substituted POMs has
been synthesized. Peacock and Weakley in 1971, first time
incorporated a lanthanide cation into the lacunary POMs.2
Thereafter, lanthanide substituted POMs were highly explored as
the lanthanide cations were oxophilic in nature and generally
exhibit high coordination numbers coupled with a large number of
1
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10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
intrinsic properties and applications such as Lewis acid catalysts, Results and Discussion
magnetic, electrochemistry, and luminescence properties.3 In
recent years, the focus has been shifted on the design and
synthesis of mixed transition metals (TMs) (3d or 4d) and
lanthanide cations which forms a 3d-4f or 4d-4f heterometallic
species. It is due to the fact that the development of this
heterometallic class combines the properties of both 3d and 4f
compounds, which makes it important in the field of catalysis,
molecular magnets,4 and molecular absorption.5 The study of
mixed-metal polyoxometalates remained in grey area a decade
ago, however, this field has now been much explored in the
search of new structures with enhanced applications.6 It is seen
that the 4f cations show more electrophilic reactivity towards
POMs as compared to the TM cations, hence the synthetic
conditions are of utmost importance as there is a competition
between the oxophilic 4f cations and relatively less reactive 3d
metal cations. Thus, in most cases, an amorphous precipitate is
obtained instead of crystalline material making it difficult and
Syntheses and Structure
All the compounds 1a–11a were synthesized by a one-pot
reaction procedure by
Ln(NO3)3·nH2O
reacting Zn(NO3)2·6H2O and
with divacant
K14[P2W19O69(H2O)]∙24H2O
precursor in an aqueous potassium chloride solution. All the
single crystalline materials were isolated as potassium salts and
characterized by different analytical techniques. The FT-IR
spectra show that all the molecular nanoclusters are very similar.
Single crystal X-ray diffraction analyses of all the polyanions
reveal that title compounds are isostructural and crystallize in the
orthorhombic crystal system with space group Iba2 (Table 1). The
structure of the polyanion consists of two (1,5) isomer of α-type
divacant Keggin anion {PW10O36}, four Zn2+ cations, and one Ln3+
cation. The α-type {PW10O36} unit is derived from the removal of
two WO6 octahedra from the parent α-Keggin anion.
challenging to synthesize
a single crystalline material of
heterometallic aggregate.7 However, several compounds of such
heterometallic class were isolated, in which most of the reported
compounds are organic-inorganic hybrids which were
synthesized by using organic ligands mostly under hydrothermal
conditions with a few examples reported under mild conditions.8
There are also some examples in which both 3d and 4f metals are
present within the POM skeleton.9-17 The heterometallic POM
based on lone-pair containing tungstoantimonates (III) were also
As reported in the previous literature, it is known that
K14[P2W19O69(H2O)] is a labile POM ligand which can interconvert
into other stable species to form different mixture of isomers under
the variation of pH along with the presence of potassium
ions.3g,3i,23 The monolacunary Keggin type [PW11O39K]6– species
is formed at lower pH which further reacts with divalent zinc ions
to form α-species of di-Zn substituted Keggin type
tungstophosphate [PZn2W10O38(H2O)2]7–. It is unstable in an
aqueous solution which slowly changes to tetranuclear Zn-
reported
by
Artetxe
et
al.
of
the
formula
[Sb7W36O133Ln3M2(OAc)(H2O)8]17– (Ln3M2; Ln = LaIII – GdIII, M =
CoII; Ln = CeIII, M = NiII and ZnII) by reacting 3d metal di-
substituted Krebs-type tungstoantimonates (III) with early
lanthanides.18 Thereafter, our group have also focused in
synthesizing heterometallic POM nanoclusters in a one-pot
procedure under mild reaction conditions.19-21 Notably, the
research work on synthesis of 3d-4f POMs have progressed over
the years to become an emerging field possessing potential
applications.22
substituted species [Zn4(OH2)2(PW9O34)2]10– 24
. We have seen that
the presence of lanthanide cation stabilizes the di-Zn substituted
tungstophosphate which results in the formation of Ln
sandwiched polyanion and its subsequent isolation as single
crystal material (Fig. 1). In the title polyanions, the central P atoms
have a tetra-coordination environment. The P–O bond lengths
vary from 1.48 (4) to 1.59 (2) Å and the O–P–O angles from 105.5
(10)° to 113.0 (2)°. Each zinc ion is hexa-coordinated which is
present in the cavity of the dilacunary {α-PW10O36} unit in an
octahedral geometry. The coordination sites of Zn ion are satisfied
by two oxygen atoms of WO6 octahedra, one oxygen atom which
is further coordinated with the heteroatom, one terminal water
molecule and two oxygen atoms that are coordinated to the
lanthanide cation. The various bond lengths and O–P–O bond
angles are summarized in Table S1 and S2 respectively. The
lanthanide cation is eight coordinated with its coordination sites
satisfied by four axial oxygen atoms of each hetero Keggin anions.
Thus, two α-type (1,5)-isomer of hetero Keggin {PZn2W10O36}
units are connected through eight {Ln–μ3(O)–Zn} bonds. In other
words, the heterometallic Zn4-Ln core center is stabilized by the
two divacant {α-PW10} moieties. Lanthanide ion has square
antiprismatic geometry with C2 symmetry. The Ln–O bond lengths
vary in the range from 2.30 (4) to 2.51 (2) Å. Notably, all the
bridging O atoms in between the lanthanide and zinc ions exhibits
a μ3-bridging with LnIII, ZnII, and WVI centers, respectively. The
Bond Valance Sum (BVS) calculation25 was also performed on the
title polyanions which suggest none of the oxygen atoms of the
divacant {α-PW10O36} units were protonated. The net charge of
the title polyanion [Ln{PZn2W10O38(H2O)2}2] was calculated to be
−11 which was compensated by the potassium cations. Each zinc
metal ion possesses one terminal water molecule (O23 and O38).
The BVS calculation also shows that zinc exists in +2 and
lanthanide in +3 oxidation state which is illustrated in Table S3.
Herein, we report the synthesis of
a purely inorganic
heterometallic 3d-4f nano-aggregate under mild reaction
conditions. We have isolated a series of heterometallic lanthanide
sandwich (1,5)-isomer of di-Zn substituted α-Keggin type
tungstophosphate [Ln{PZn2W10O38(H2O)2}2]11– (Ln = NdIII, SmIII,
EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII). All these
nanoclusters were synthesized by a one-pot reaction procedure
by using divacant precursor K14[P2W19O69(H2O)]·24H2O,
Ln(NO3)3·nH2O and Zn(NO3)2·6H2O in aqueous potassium
chloride solution. The potassium salts of solid single crystalline
material were isolated and used for further characterization with
different analytical techniques including SC-XRD, FT-IR, ESI-MS,
ICP-AES, solid UV/Vis, solid photoluminescence spectroscopy,
P-XRD and TGA. The synthesized complexes were used as
catalysts for the oxidation of thioethers. It is also worth mentioning
that the catalyst is stable and can be recovered even after five
consecutive cycles of reaction with a high turn over frequency of
6250 h-1. The compounds were also analyzed for their magnetic
properties of which Gd, Tb, Dy, Er, and Yb based complexes
show single-molecule magnetic behavior.
2
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10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
Interestingly, it was seen that if the mother liquor was left over for
more than a month after complete crystallization, it eventually
leads to the formation of few crystals of tetramer
[Zn4(OH2)2(PW9O34)2]10– compounds which were isolated as a
side product. The di-substituted {PZn2W10} Keggin anion usually
forms a mixture of isomers {(1,2), (1,4), (1,5), (1,6) and (1,11)}26
but here we have isolated explicitly one isomeric species (1,5) of
di-Zn substituted Keggin anion.
4I9/2→4F3/2
, , , ,
4I9/2→2H11/2 4I9/2→4F9/2 4I9/2→4I15/2 4I9/2→4I13/2 and
4I9/2→4I11/2 transitions of the NdIII ion (Fig. S2).28
In the absorption spectrum of Dy-6a compound, eight absorption
bands are observed in which four weak intense bands are
observed in the visible region at around 388, 427, 454 and 474
nm, which are assigned to H15/2→4F7/2,4I13/2
6H15/2→4I15/2 and H15/2→4G11/2 transitions respectively. Four
relatively higher intense bands at 756, 807, 907 and 982 nm are
observed in the near IR region. These are ascribed to 6H15/2→6F3/2
6H15/2→6F5/2, H15/2→6F7/2 and H15/2→6H5/2 transitions of the DyIII
ion, respectively (Fig. S3).28b,29
6
, ,
6H15/2→4F9/2
6
,
6
6
The Ho-7a compound exhibits six absorption bands at around 422,
454, 475, 486, 542 and 649 nm in the absorption spectrum which
arises due to transitions from the ground state 5I8 to various
excited state energy levels. These bands are assigned to 5I8→5G5,
5I8→5F1,5G6, 5I8→3K8,5F2, 5I8→5F3, 5I8→5F4,5S2 and 5I8→5F6
transitions of the HoIII ion respectively. The high intense
5I8→5F1,5G6 transition contributes to the color of this species (Fig.
S4).28b,30
For the Er-8a compound, displays seven absorption bands which
are centered at 382, 409, 451, 491, 524, 550 and 653 nm. All
4
transitions of the Er3+ ion occur due to I15/2 ground state to the
excited states energy levels which can be assigned to
Figure
1.
Schematic
representation
of
nanoclusters:
4I15/2→4G11/2, 4I15/2→2H9/2, 4I15/2→4F3/2,5/2, 4I15/2→4F7/2, 4I15/2→2H11/2
,
[Ln{PZn2W10O38(H2O)2}2]11– (Ln = NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII,
YbIII, and LuIII) synthesized by using starting precursor [P2W19O69(H2O)]14-
(Colour code; pink: Ln; yellow: Zn; dark teal: W polyhedra; bright green: P; red:
O; aqua: H2O).
4
4I15/2→4S3/2 and I15/2→4F9/2 transitions, respectively. The pink
color of the Er3+ ion is almost entirely due to the I15/2→2H11/2
4
transition at 524 nm in the green region (Fig. S5).31,32 The three
absorption bands are found in the absorption spectrum of Tm-9a
compound which centered at around 474, 697 and 793 nm in the
visible region. These bands are ascribed due to the transitions
from the 3H6 ground state to the different excited state energy
levels 1G4, 3F3 and 3F4 of the TmIII ion, respectively (Fig. S6).29a
FT-IR Spectroscopy
The FT-IR spectra of all the compounds were recorded on KBr
pellets with a PerkinElmer BX spectrometer. In the FT-IR
spectroscopy, all the molecular clusters 1a–11a show similar
stretching frequency with a slight shift in the position of the
vibration bands and their comparison spectra clearly indicates
that all polyanions are very similar (Fig. S1). Polyanions show four
characteristic antisymmetric stretching vibration bands including
antisymmetric stretching modes of νas(P–Oa), terminal νas(W–Ot),
corner sharing νas(W–Ob), edge sharing νas(W–Oc) bonds in the
fingerprint region (1200 – 400 cm‒1) of the POM chemistry.27 The
three bands at around 1076, 1052 and 1036 cm–1 are due to the
antisymmetric stretching vibration of νas(P–Oa) and band at 946
cm–1 is attributed to terminal νas(W–Ot). The vibration band at
around 890 cm–1 corresponds to corner shared νas(W–Ob) and the
two bands at 812 and 759 cm–1 are assigned to the edge shared
νas(W–Oc) bonds.
Photoluminescence Spectroscopy
The photoluminescence (PL) spectra of all the compounds were
recorded upon photo-excitation at room temperature, but we have
successfully recorded emission spectra for Sm-2a, Eu-3a, Tb-5a,
and Dy-6a compounds.
The PL spectrum of the Sm-2a compound shows four
characteristic emission peaks at around 567, 610, 656 and 712
nm, in the visible region on photo-excitation at 377 nm. These
4
peaks are due to the corresponding transitions from the G5/2
excited state energy level to different ground state energy levels,
6
6
6H5/2 (zero-zero band), H7/2 (magnetic dipole transition), H9/2
(electric dipole transition) and 6H11/2 of the SmIII ion, respectively.
The orange color of the Sm-2a compound is due to the relatively
UV/Vis Spectroscopy
high intense G5/2→6H7/2 transition (Fig. 2).30,32 Futhermore, the
4
fluorescence quantum yield (Q.Y.) of Sm-2a has been calculated
with respect to the reference standard dye Methylene Blue (MB).
The fluorescence Q.Y. w.r.t. standard MB of Sm-2a is found to be
15%. On the photo-excitation at 394 nm, Eu-3a compound
displays four emission peaks situated at about 538 (green), 594
(orange), 613 (red) and 708 (deep-red) nm. These peaks arise
The UV/Vis spectra of all the polyanions were recorded in the
solid state. We have successfully obtained the solid-state
absorption spectra for Nd-1a, Dy-6a, Ho-7a, Er-8a, and Tm-9a
POMs.
The solid-state absorption spectrum of the Nd-1a compound
shows eight absorption bands. Six bands are observed at around
515, 529, 586, 638, 692 and 750 nm in the visible region, whereas
5
5
5
5
due to the D1→7F1, D0→7F1, D0→7F2 and D0→7F4 electronic
transitions of the Eu3+, respectively. The 5D0→7F1 transition is
5
magnetic-dipolar whereas D0→7F2,4 transitions are the electric-
two bands at 806 and 878 nm are found in the near IR region.
dipolar transition. The 5D0→7F1 transition is very weak, the
4
These bands can be assigned to the I9/2→2K13/2
,
4I9/2→4F5/2
,
intensity of this transition is independent of their local environment
3
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10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
Table 1. Crystal data and refinement
Nd-1a
Sm-2a
Eu-3a
Gd-4a
Tb-5a
Dy-6a
Polyanion
K11NdZn4P2W20
O103H54
K11SmZn4P2W20O103
H54
K11EuZn4P2W20O103
H
K11GdZn4P2W20
O
K11TbZn4P2W20O102
H52
K11DyZn4P2W20O103
H54
Emp. Formula
103H54
54
6276.99
Ortho-rhombic
Iba2
6283.11
Ortho-rhombic
Iba2
6284.72
6290.00
Orthorhombic
Iba2
6273.66
Orthorhombic
Iba2
6295.25
Orthorhombic
Iba2
Form. weight
Crystal system
Space group
a/Å
Ortho-rhombic
Iba2
19.8088(5)
27.4724(7)
18.4100(5)
27.3399(11)
19.7194(8)
18.4359(6)
19.6985(7)
27.3352(9)
18.5101(7)
19.7422(7)
27.3170(9)
18.5223(6)
19.7507(4)
27.2824(6)
18.5728(4)
19.6700(9)
27.2296(11)
18.6077(8)
b/Å
c/Å
α [⁰] = β[⁰] = γ[⁰]
90
10018.6(4)
4
90
9939.3(7)
4
90
9967.0(6)
4
90
9989.1(6)
4
90
10007.9(4)
4
90
9966.4(7)
4
V/Å3
Z
T/K
298.15
4.019
298.15
4.013
25.157
1.026
10452.0
62446
9438
293(2)
4.045
25.132
1.053
10584.0
46411
9233
298.15
3.908
24.883
1.051
10202.0
61515
9481
298.15
4.034
298.15
4.074
25.257
1.043
10660.0
64554
9452
ρcalcd [g cm-3]
μ/mm-1
24.895
1.028
25.110
1.061
Goodness-of-fit
F(000)
10572.0
65067
9514
10592.0
65599
9509
Ref. collected
Independent
reflections
0.0996
0.1016
0.0695
0.0883
0.0589
0.0593
Rint
Parameters
570
552
560
555
570
370
R[I>2σ(I)] [a]
0.0571
0.0434
0.0376
0.0426
0.0290
0.0299
Rw (all data) [b]
0.1425
0.0910
0.0872
0.0970
0.0633
0.0658
Largest diff.
peak/hole / e Å-3
2.10/-1.77
1.90/-1.18
1.62/-1.33
2.54/-1.20
1.15/-1.08
1.27/-1.23
Ho-7a
K11HoZn4P2W20
O103H54
Er-8a
K11ErZn4P2W20O103
H54
Tm-9a
Yb-10a
Lu-11a
K11LuZn4P2W20O102
H52
Polyanion
K11TmZn4P2W20O103
K11YbZn4P2W20
O
Emp. Formula
H54
103H54
6297.68
6300.01
6301.69
6305.79
6289.71
Form. weight
Crystal system
Space group
a/Å
Orthorhombic
Iba2
Orthorhombic
Iba2
Orthorhombic
Iba2
Orthorhombic
Iba2
Orthorhombic
Iba2
19.6935(6)
27.2025(8)
18.6251(6)
90
19.6218(7)
27.1232(10)
18.6153(7)
90
19.7245(7)
27.2526(12)
18.7480(5)
90
19.5996(13)
27.1430(11)
18.7232(7)
90
27.0632(14)
19.7550(11)
18.6995(8)
90
b/Å
c/Å
α [⁰] = β[⁰] = γ[⁰]
V/Å3
9977.7(5)
4
9907.2(6)
4
10077.8(6)
4
9960.5(9)
4
9997.4(9)
4
Z
T/K
293(2)
298.15
4.080
298.15
4.002
298.15
4.094
293(2)
ρcalcd [g cm-3]
μ/mm-1
4.039
4.038
25.268
1.031
25.498
1.061
25.113
1.043
25.462
1.023
25.415
1.047
Goodness-of-fit
F(000)
10568.0
64770
10604.0
60832
10576.0
61791
10708.0
61207
10584.0
64953
Ref. collected
Independent
reflections
9475
9392
9206
9435
9493
0.0737
570
0.0963
570
0.1346
560
0.1707
485
0.1589
491
Rint
Parameters
R[I>2σ(I)] [a]
Rw (all data) [b]
0.0347
0.0752
1.22/-1.26
0.0422
0.0990
1.44/-1.28
0.0531
0.1284
1.87/-2.53
0.0732
0.1634
2.91/-1.98
0.0630
0.1417
2.53/-1.78
Largest diff.
peak/hole / e Å-3
[a] R =IIFoI- IFcII/IFoI. [b] Rw = [w(Fo2 -Fc2)2/w(Fo2)2]1/2
4
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10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
4
and it varies with increasing ligand field strength which is acting
on EuIII ion. The 5D0→7F2 transition is very sensitive to the
chemical bonds in the vicinity of the EuIII ion and the intensity of
this transition increases as the site symmetry of EuIII ion
decreases. So the intensity ratio of the electric dipole transition
5D0→7F2 and magnetic dipole transition 5D0→7F1 can be used for
the measurement of the coordination state and site symmetry of
the EuIII ion. For the Eu-3a compound, the intensity ratio
I(5D0→7F2)/I(5D0→7F1) is equal to 4.57, which signifies low
symmetry of the EuIII ion. The highly intense 5D0→7F2 peak at
around 613 nm is entirely responsible for the red emission of the
Eu-3a compound (Fig. 3a).29a,33 The fluorescence Q.Y. of Eu-3a
w.r.t. standard MB is found to be 4.16%.
peaks can be ascribed to F9/2→6H15/2 4F9/2→6H13/2 and
,
4F9/2→6H11/2 transitions of the DyIII ion, respectively. The yellow
emission of the Dy-6a compound is due to the relatively high
intense 4F9/2→6H13/2 transition at around 577 nm (Fig. 3b).29,30 The
fluorescence Q.Y. of Dy-6a w.r.t. standard MB is found to be
4.96%. The parameters involved in the determination of
fluorescence Q.Y. is shown in Table S4.
Powder X-ray Diffraction
The X-ray powder diffraction (P-XRD) was performed at room
temperature in the range 2θ = 5° - 50° for all the nanoclusters 1a-
11a. The P-XRD patterns matched perfectly which justifies that
the synthesized ten complexes are isostructural (Fig. S8, S9)
Furthermore, the P-XRD patterns for the fresh catalyst Dy-6a was
also compared with both the simulated and recovered catalyst
pattern. The P-XRD patterns matches perfectly which indicates
the stability of the catalyst after five cycles of reactions (Fig. S15).
HR-ESI-MS
The high-resolution electro-spray ionization mass spectrometry
(HR-ESI-MS) of 1a–11a was performed after each sample was
dissolved in CH3CN-H2O solution.
Figure 2. Photoluminescence spectra of Sm-2a on the photo-excitation at 377
nm at room temperature.
Figure 3. Photoluminescence spectra of (a) Eu-3a and (b) Dy-6a on the photo-
excitation at 394 and 370 nm, respectively, at room temperature.
The Tb-5a compound shows two weak emission peaks upon
photo-excitation at 400 nm at room temperature. These peaks
observed at around 593 and 612 nm, which are assigned to the
5
5D4→7F4 and D4→7F3 transitions, respectively (Fig. S7).28a,29b,34
The fluorescence Q.Y. of Tb-5a w.r.t. standard MB is found to be
4.2%. In the emission spectrum of the Dy-6a compound, three
emission peaks at 486 (blue), 577 (yellow), and 666 (red) nm are
found on photo-excitation at 370 nm at room temperature. These
Figure 4. (a) Negative ESI mass spectrometry of 7a and (b) expanded region
and simulated peaks for H8[Ho{PZn2W10O38}]3−
5
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10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
Fig. 4 represents an ESI-MS of 7a, signals assignable to protonic
performed some parallel experiments to check the catalytic
activity. It is seen that when the reaction is carried out in the
presence of 1.5 mmol H2O2 only, the conversion is very low,
approximately 10 % (Table 2 Entry 4). Thereafter, on increasing
the amount of catalyst from 0.08 to 0.32 mol%, both the
conversion and selectivity of sulfone also increases and hence,
the optimized catalyst amount is found to be 0.32 mol% (Table 2).
The substrate and oxidant ratio also significantly affect the
selectivity and conversion of diphenyl sulfone over the diphenyl
sulfoxide.
forms of the sandwich species such as [H9Ho{PZn2W10O38}2]2–,
[H8Ho{PZn2W10O38}2]3–,
[H7Ho{PZn2W10O38}2]4–,
and
[H6Ho{PZn2W10O38}2]5– are observed together with their
dehydrated species such as [H5Ho{PZn2W10O38}{PZn2W10O37}]4−.
In the case of other complexes, signals assignable to
[H8−x{Ln{PZn2W10O38}2](3+x)− are observed (Fig. S10), indicating
that the lanthanide sandwiched species are stable in the solution.
Peaks assignable to fragments such as [PZn2W10O36]3−, the
dehydrate form of [H4PZn2W10O38]3− is also observed. Peaks
assignable to [H7Zn4(PW9O34)2]3– and [H5Zn4(PW9O34)2]5– are also
observed. The [Zn4(PW9O34)2]10– has tetra-Zn core sandwiched by
two [PW9O34]9–, which might be a side product or a decomposed
product in solution because it is known that [PW10O38Zn2(H2O)2]7–
The ratio of standard substrate and oxidant is 1:3 for 100%
selectivity of diphenyl sulfone which decreases as the ratio of
oxidant is reduced (Table 2, Entry 1, 5, 6, 7). To verify the
catalytic activity of catalyst, we have also performed some parallel
reactions. Oxidation were carried out in the presence of the POM
transforms to the [Zn4(PW9O34)2]10– 23,24
and longer reaction time
,
increases the amount of [Zn4(PW9O34)2]10– (see synthesis and
structure section).
precursor
K14[P2W19O69(H2O)]·24H2O,
lanthanide
salt
Dy(NO3)3·xH2O and Zn(NO3)2·6H2O salt. The conversion was
found to be very less in case of lanthanide salt and transition
metal salt, but the lacunary POM precursor shows good
conversion, however, the selectivity of diphenyl sulfone was
significantly low (Table S5). All these parallel experiments show
that the catalyst Dy-6a shows excellent catalytic properties in
presence of H2O2 (Table 2). The reaction temperature also plays
an important role during the reaction. When the reaction was
carried out at room temperature, the conversion is low, but on
increasing the temperature, the conversion and selectivity both
increases. The optimized temperature for the reaction is 40 °C.
Catalytic Application
Polyoxometalates can be used as catalysts due to their vital
properties such as redox properties, proton-transfer reactions,
and structural variety. The polyoxometalates are widely used as
catalyst for the oxidation of thioethers especially in H2O2-based
oxidation reactions since no toxic by-products are produced
during the reaction.35 Nowadays, much attention has recently
been focused on the use of the POMs as catalysts in the oxidation
reaction of organic thioether compounds for the selective
syntheses of sulfoxides and sulfones which are used as synthetic
intermediates in pharmaceutical field, sulfoxidation reactions,
chemical industry, medicinal chemistry, and biochemistry. The
homogeneous catalysis reactions for the POMs are remarkably
efficient, but they have common drawback such as separation and
reuse of the catalysts are very difficult. Due to this, the future
applications of POMs will require methods for recovery and
recycling of catalysts. Hence, heterogeneous catalyst is much
more beneficial wherein, the catalyst can be easily recycled and
reused for further reactions. Herein, we have used mixed
lanthanide-transition metal-substituted POM complexes as
catalyst for the oxidation reaction of thioethers in the presence of
H2O2 as the oxidant. Initially, we have screened all the catalysts
under standard conditions (biphenyl sulfide 0.5 mmol, H2O2 (30 %
aqueous), catalyst loading 0.32 mol%, temperature, 40 °C, 30 min,
acetonitrile 1 mL). All the catalysts show excellent catalytic activity
(Fig. S12) for the oxidation of thioethers. Thereafter, for further
catalysis reaction we used Dy-6a as model catalyst due to its high
yield during the synthesis and selectivity for the sulfone. The
conversion and selectivity of sulfoxide (RSOR’) and sulfone
(RSO2R’) were investigated by Gas Chromatography using the
internal standard method (GC spectra Fig. S13).
Table 2. Oxidation of biphenyl sulfide by using catalyst Dy-6a[a]
Entry
Temp
(°C)
H2O2
Catalyst
loading
(mol %)
Convers
ion (%)[b]
Selectivity (%)[c]
Time
(min)
(mmol)
(PhSOPh) (PhSO2Ph)
1
2
40
40
40
40
40
40
40
40
40
25
1.5
1.5
1.5
1.5
1.0
0.5
0.0
1.5
1.5
1.5
0.32
0.16
0.08
0.00
0.32
0.32
0.32
0.32
0.32
0.32
100
100
100
10
0
100
85
30
40
26
15
45
73
90
40
30
30
30
30
30
30
30
10
20
30
15
70
60
69
85
55
27
10
60
3
4
5
80
6
50
7
10
8
100
100
40
9
10
Catalytic reaction of the Dy-6a were analysed in the oxidation of
PhSPh as a model substrate using aqueous H2O2 in acetonitrile.
The reactant biphenyl sulfide completely converts into the
corresponding diphenyl sulfone within 30 min with 100%
selectivity at 40 °C in the presence of 1 mL of acetonitrile, 1.5
mmol H2O2, and 0.32 mol% of catalyst Dy-6a. We have varied the
various parameters for the reaction such as catalyst mol%,
oxidant amount, reaction time and temperature. All these
parameters affect the reaction condition strongly. We have also
[a] Reaction conditions: biphenyl sulfide 0.5 mmol, oxidant H2O2 (30 % aqueous),
0-1.5 mmol, catalyst Dy-6a loading 0.08-0.32 mol%, temperature 25-40 °C, 30
min, acetonitrile 1 mL. [b] Conversion based on substrate consumption and
determined by GC-FID using an internal standard technique. [c] The Selectivity
of (PhSOPh/ PhSO2Ph) is determined by GC.
6
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10.1002/ejic.202100528
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Under the optimized conditions, we have oxidized various
derivatives of thioethers into corresponding sulfone with 100%
selectivity. Electron-donating group containing aromatic
thioethers such as 4-methylthioanisol and 4-methoxythioanisol
shows excellent selectivity and electron-withdrawing group
containing aromatic thioethers such as 4-cynothianisol, 4-
nitrothianisol (Table 3) also shows very good selectivity. It was
also observed the position of the substituents on the aromatic ring
also affects the selectivity of sulfone over sulfoxide (Table 3).
It might be due to the stability of aromatic system and larger steric
hindrance. The oxidation of dibenzothiophene show less
selectivity for sulfone as compared to alkyl aryl thioethers (Table
3). The compound with open chain such as diallyl sulfide also
oxidized with excellent selectivity of sulfone within 30 minutes.
In addition, a recycling test was also performed to evaluate the
catalytic performance for the catalyst during the oxidation reaction
under optimal conditions (Fig. 5). A hot filtration experiment was
performed for the heterogeneity of the oxidation reaction. We
have removed the catalyst after 10 min by filtration method and
the reaction was continued. It was seen that a small conversion
of product was obtained indicating that the reaction system is
heterogeneous. In this heterogeneous system, the catalyst was
collected by filtration after the completion of the reaction, washed
with ethyl acetate, dried and reused in the next run. The recycled
catalyst can be used up to five consecutive runs and thereafter,
the conversion and selectivity slightly decreases. The recycled
catalyst was characterized by FT-IR during each consecutive run
and it was observed that the FT-IR spectra of all the cycles were
similar to that of the fresh catalyst (Fig. S14). Along with the FT-
IR spectra, the P-XRD pattern of the recovered catalyst also
matches with the pattern of the fresh catalyst (Fig. S15). Further,
we have also calculated turn over frequency (TOF) for the catalyst
and was found to be 6250 h−1 which is much higher than the other
reported POM complexes (Table S6). This indicates our catalyst
shows excellent catalytic property.
peroxo linkage intermediate and rapidly react with sulphides to
form corresponding oxidized products.
Table 3. Selective oxidation of various alkyl and aryl derivative thioethers by
using the catalyst Dy-6a
Conversion
(%)
Selectivity
(%)
Time
(min)
Entry
Substrate
RSOR'
RSO2R'
1
2
100
100
0
100
30
60
0
100
100
100
100
100
86
3
4
5
6
7
100
100
100
100
86
0
0
0
0
0
60
60
60
60
60
8
9
100
100
100
7
0
0
93
60
30
60
100
100
10
[a] Reaction conditions: Substrate 0.5 mmol, oxidant H2O2 (30 % aqueous) 4
mmol, catalyst 0.32 mol%, temperature 40 °C, acetonitrile 1 mL. [b] Conversion
based on substrate consumption and determined by GC-FID using an internal
standard technique. [c] The selectivity (RSOR’/RSO2R’) is determined by GC.
Magnetic Properties
The temperature dependence of the products of the molar
magnetic susceptibility and temperatures (χmT) for Nd-1a, Sm-2a,
Eu-3a, Gd-4a, Tb-5a, Dy-6a, Ho-7a, Er-8a, Tm-9a, and Yb-10a,
after deducting the diamagnetic components calculated using
Pascal's constants, are shown in Fig. 6. The measurements were
performed with a Quantum Design MPMS-5S superconducting
quantum interference device (SQUID) magnetometer using
polycrystalline samples under direct current (DC) magnetic field
of 5 kOe in the temperature range of 2 – 300 K. The chemical
formulas listed in Table 1 were used to determine molecular
weights of all compounds.
Figure 5. Catalytic runs for the thioethers oxidation reaction under standard
condition.
To the best of our knowledge, the catalytic activity for the
oxidation of thioethers using heterometallic 3d-4f POM has been
investigated for the first time. The hypothetical mechanism for
catalysis is given in Figure S20. According to the proposed
hypothetical mechanism, the synthesized POM complexes have
negatively charged oxygen atoms which activate H2O2 by forming
For all compounds, the χmT values were almost constant down to
approximately 70 K and then decreased as the temperature was
lowered further. The χmT values for all compounds at 300 K are
7
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10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
shown in Table S7. The obtained values were less than those
estimated from the isolated lanthanide ions, except for Yb-10a.
The isothermal magnetization for all compounds was measured
at 2 K (Fig. S16). The magnetization values were monotonically
Ueff/kB and τ0 for Er-8a were estimated to be 9.08(17) K and
5.68(20)×10−5 s, respectively. As shown in Fig. S17, similar
behavior of χm' and χm'' signals was observed for Yb-10a, and the
fitted Ueff/kB is 10.7(11) K with τ0 = 4.4(10) × 10−5 s. On the other
increased to around ±10 kOe, and they almost reached saturation, hand, for Gd-4a and Tb-5a, the χm'' peaks at 2 K shifted to higher
except for Nd-1a, Sm-2a, Eu-3a, and Ho-7a.
frequencies (629 and 794 Hz for Gd-4a and Tb-5a, respectively)
compared to those for Er-8a and Yb-10a (Fig. S18). In addition,
linear behaviors were observed in their Arrhenius plots. The
results of linear regression for both plots revealed the values for
Recently, single-molecule magnets (SMMs) have been studied
extensively in clusters possessing lanthanide ions.36 Thus, we
performed measurements of the temperature-dependent
alternating current (AC) magnetic susceptibility to investigate
whether these POMs including one lanthanide ion exhibit
behaviors similar to SMMs for Gd-4a, Tb-5a, Dy-6a, Ho-7a, Er-
8a, Tm-9a, and Yb-10a. In-phase (χm') signals did not show
frequency dependence, and the χm' values increased with
decreasing temperature in the low-temperature region.
effective energy barriers and relaxation times with Ueff/kB
=
6.30(39) K, τ0 = 1.22(15) × 10−5 s for Gd-4a and Ueff/kB = 4.54(19)
K, τ0 = 1.92(12) × 10−5 s for Tb-5a (Fig. 8), respectively. It should
be noted that it is difficult to analyze the magnetic behavior for Dy-
6a because two-component semi-circles were observed in the
Cole–Cole plots (Fig. S19), as reported in several papers on DyIII-
based SMMs.39
For seven compounds (Gd-4a, Tb-5a, Dy-6a, Ho-7a, Er-8a, Tm-
9a, and Yb-10a), it was revealed that POMs containing GdIII,
DyIII,TbIII, ErIII, and YbIII ions exhibit SMM-like behavior with a slow
relaxation process.
Figure 6. Temperature dependence curves of the products of molar magnetic
susceptibility and temperatures (χmT) for Nd-1a, Sm-2a, Eu-3a, Gd-4a, Tb-5a,
Dy-6a, Ho-7a, Er-8a, Tm-9a, and Yb-10a.
On the other hand, the values of out-of-phase (χm'') were close to
zero in the measured temperature range. Thus, the frequency and
temperature dependence of AC magnetic susceptibility were
measured under a static bias field of 1 kOe in which the
magnetization did not reach saturation magnetization. The
measurements were carried out in the temperature range of 2 to
5 K with a temperature step increment of 0.25 K. Slow relaxation
of magnetization was observed for Gd-4a, Tb-5a, Dy-6a, Er-8a,
and Yb-10a, whereas Ho-7a and Tm-9a did not show the slow
relaxation of magnetization. Figures 7a and 7b show the
frequency- and temperature-dependent χm' and χm'' signals for Er-
8a. The frequency-dependent χm'' peaks could be found between
79.4 Hz (2 K) and 794 Hz (5 K). In addition, the Arrhenius plot,
which is produced using the fitting results of the Cole–Cole plots,37
exhibited curvature (Figures 7c and 7d). This suggests that
multiple relaxation processes exist in Er-8a.37 Thus, multi-process
fitting, including direct, Raman, and Orbach processes, was
conducted using the following equation:
Figure 7. AC magnetic susceptibility measured at a static bias field of 1 kOe at
various temperatures for Er-8a. Frequency-dependent (a) in-phase (χm') signals,
(b) out-of-phase (χm'') signals, (c) Cole–Cole plots and (d) Arrhenius plots. The
black solid line describes the fitted curve.
1 = 퐴푇 + 퐵푇푛 + 휏0−1 exp(− 푈푘푒푓푓
) (1)
휏
퐵푇
where AT, BTn, and τ0−1exp(−Ueff/kBT) represent direct, Raman,
and Orbach relaxation processes, respectively.38b,38c The Ueff/kB
and τ0 values describe the effective energy barrier and a
relaxation time, respectively. According to the analysis (Table S8),
Figure 8. AC magnetic susceptibility measured at a static bias field of 1 kOe at
various temperatures for Tb-5a. Frequency-dependent (a) in-phase (χm') signals,
(b) out-of-phase (χm'') signals, (c) Cole–Cole plots and (d) Arrhenius plots. The
black solid line describes the fitted curve.
8
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10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
superconducting quantum interference device (SQUID) magnetometer
using polycrystalline samples under direct current (DC) and alternating
current (AC) magnetic field.
From our results, it is not possible to conclude on the mechanism
that can explain why only five of the seven complexes
investigated show SMM behavior. Furthermore, we can notice
that Gd-4a is one of the rare reported SMM complexes.40 In
previous result by Yoshida et al. the slow magnetization in Gd ion
was induced by the creation of bond between Gd and Pt or Pd
diamagnetic ions. A similar mechanism, between Gd and W, can
be considered as the origin of the SMM properties observed in
our Gd complex.
Syntheses and Characterization
Synthesis of K11[Nd{PZn2W10O38(H2O)2}2]·23H2O (Nd-1a)
In 25 mL of 0.25 M KCl solution, 0.089 g Zn(NO3)2·6H2O (0.3 mmol) and
0.044
g Nd(NO3)3·6H2O (0.1 mmol) were added. 0.566 g of
K14[P2W19O69(H2O)]·24H2O (0.1 mmol) was added subsequently. The
reaction mixture was stirred continuously at 80 °C for 1 h. During heating,
the solution turned from milky turbid to clear. The solution was cooled to
room temperature and any precipitate formed was removed by filtration.
After about a few hours, needle-like light violet crystals were obtained.
Yield: 0.115 g (20%) (based on K14[P2W19O69(H2O)]∙24H2O). The numbers
of crystal water molecules have been determined by thermogravimetric
analysis. FT-IR (with KBr pellets): 1070(s), 1052(s), 1036(s), 946(s),
888(s), 808(s), 755(m), 699(w), 620(w), 485(m), 438(w) cm–1. Elemental
analysis (%) for K11NdZn4P2W20O103H54; calcd. (found): Nd 2.32 (2.23), Zn
4.20 (4.37), W 59.09 (58.83), P 1.00 (1.07), K 6.89 (6.92).
Conclusion
A
series of eleven heterometallic 3d-4f tungstophosphate
nanoclusters [Ln{PZn2W10O38(H2O)2}2]11– (LnIII = Nd, Sm, Eu, Gd,
Tb, Dy, Ho, Er, Tm, Yb, and Lu) have been synthesized by a one-
pot
reaction
procedure
using
dilacunary
K14[P2W19O69(H2O)]·24H2O precursor in an aqueous potassium
chloride solution. The isolated single crystalline materials were
characterized by various analytical techniques such as SC-XRD,
FT-IR, ESI-MS, elemental analysis by ICP-AES, P-XRD, solid
UV/Vis, solid photoluminescence spectroscopy, and TGA. The
SC-XRD analysis of all the polyanions show that all the
polyanions are isostructural and contains (1,5) isomer of di-Zn
substituted α-Keggin type tungstophosphates. The stability of the
catalyst was confirmed by P-XRD. The molecular complexes Sm-
2a, Eu-3a, Tb-5a, and Dy-6a show good photoluminescence
behavior at room temperature. The synthesized complexes were
also used to investigate the catalytic activity for the oxidation of
thioethers which can be regarded as excellent catalyst.
Furthermore, the magnetic properties of the complexes revealed
that Gd-4a, Tb-5a, Dy-6a, Er-8a, Yb-10a behave as single
molecule magnets.
Synthesis of K11[Sm{PZn2W10O38(H2O)2}2]·23H2O (Sm-2a)
Compound Sm-2a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.044 g Sm(NO3)3·6H2O (0.1
mmol) instead of Nd(NO3)3·6H2O. Colorless needle-shaped crystals were
obtained after about a few hours. Yield: 0.285 g (51%) (based on
K14[P2W19O69(H2O)]∙24H2O). The numbers of crystal water molecules
have been determined by thermogravimetric analysis. FT-IR (with KBr
pellets): 1072(s), 1052(s), 1036(s), 946(s), 890(s), 811(s), 759(m), 692(m),
620(w), 486(m), 432(w) cm–1
.
Elemental analysis (%) for
K11SmZn4P2W20O103H54; calcd. (found): Sm 2.45 (2.28), Zn 4.26 (4.33), W
58.89 (58.61), P 1.01 (1.15), K 6.99 (6.87).
Synthesis of K11[Eu{PZn2W10O38(H2O)2}2]·23H2O (Eu-3a)
Compound Eu-3a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.043 g Eu(NO3)3·5H2O (0.1
mmol) instead of Nd(NO3)3·6H2O. After about a few hours needle-like
colorless crystals were obtained. Yield: 0.278 g (49%) (based on
K14[P2W19O69(H2O)]∙24H2O). The numbers of crystal water molecules
have been determined by thermogravimetric analysis. FT-IR (with KBr
pellets): 1072(s), 1052(s), 1036(s), 946(s), 891(s), 812(s), 759(m), 690(m),
Experimental Section
Materials and analytical methods
The potassium salt of the divacant K14[P2W19O69(H2O)]·24H2O precursor
was prepared according to the published literature procedure and
confirmed by FT-IR spectroscopy.23 All other chemicals were commercially
purchased and used without further purification. The FT-IR spectra of all
the compounds were recorded with a Perkin-Elmer BX spectrometer on
the KBr pellets. Single crystal X-ray diffraction data were collected on an
Xcalibur Oxford diffractometer operated at 50 kV and 40 mA (Mo-Kα
radiation). Solid-state UV/Vis spectra were recorded on a Thermo
Scientific Evolution 300 spectrometer. Photoluminescence spectra were
recorded on a Fluorolog Horiba Jobin Yvon spectrometer at room
temperature. Thermogravimetric analysis (TGA) measurements were
618(w), 486(m), 430(w) cm–1
.
Elemental analysis (%) for
K11EuZn4P2W20O103H54; calcd. (found): Eu 2.41 (2.32), Zn 4.14 (4.23), W
58.18 (57.76), P 0.98 (1.08), K 6.79 (6.95).
Synthesis of K11[Gd{PZn2W10O38(H2O)2}2]·23H2O (Gd-4a)
Compound Gd-4a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.045 g Gd(NO3)3·6H2O (0.1
mmol) instead of Nd(NO3)3·6H2O. Colorless needle-shaped crystals were
obtained after about a few hours. Yield: 0.253 g (45%) (based on
K14[P2W19O69(H2O)]∙24H2O). The numbers of crystal water molecules
have been determined by thermogravimetric analysis. FT-IR (with KBr
pellets): 1076(s), 1054(s), 1038(s), 946(s), 889(s), 812(s), 756(m), 692(m),
performed with
a TG/DTA Instrument DTG-60 Shimadzu in the
temperature range of 25 – 600 °C in a nitrogen atmosphere with a heating
rate of 5 °C/min. Elemental analyses were performed on an ICP-AES
instrument, ARCOS from M/s Spectro Germany. Powder X-ray diffraction
was performed by using Rigaku X-ray diffractometer at 298 K in the range
of 2θ = 5° - 50°. The catalysis experiment for the oxidation of thioethers
was carried out using Gas Chromatography (GC Plus 2010 Shimadzu).
High-resolution ESI-MS was recorded on an LTQ Orbitrap XL (Thermo
Fisher Scientific) with an accuracy of 3 ppm. Five mg of each sample was
dissolved in 5 mL of H2O, and the solutions were diluted by CH3CN (final
concentration: ca. 10 mg/mL). Peak assignments were performed by
comparing both isotropic distributions and m/Z values (difference were
less than 3 ppm) of obtained signals and simulated signals. The magnetic
measurements were performed with a Quantum Design MPMS-5S
618(w), 486(m), 428(w) cm–1
.
Elemental analysis (%) for
K11GdZn4P2W20O103H54; calcd. (found): Gd 2.48 (2.38), Zn 4.12 (4.51), W
57.96 (57.61), P 0.98 (1.12), K 6.76 (6.89).
Synthesis of K11[Tb{PZn2W10O38(H2O)2}2]·22H2O (Tb-5a)
Compound Tb-5a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.043 g Tb(NO3)3·5H2O (0.1
mmol) instead of Nd(NO3)3·6H2O. Light green color needle-shaped
crystals were obtained after about a few hours. Yield: 0.295 g (52%)
9
This article is protected by copyright. All rights reserved.

10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
(based on K14[P2W19O69(H2O)]∙24H2O). The numbers of crystal water
molecules have been determined by thermogravimetric analysis. FT-IR
(with KBr pellets): 1074(s), 1052(s), 1036(s), 946(s), 890(s), 812(s),
758(m), 692(m), 618(w), 486(m), 418(w) cm–1. Elemental analysis (%) for
K11TbZn4P2W20O102H52; calcd. (found): Tb 2.53 (2.46), Zn 4.17 (4.08), W
58.62 (58.95), P 0.99 (1.08), K 6.84 (6.89).
pellets): 1076(s), 1054(s), 1036(s), 947(s), 891(s), 811(s), 760(m), 699(m),
618(w), 487(m), 428(w) cm–1
.
Elemental analysis (%) for
K11YbZn4P2W20O103H54; calcd. (found): Yb 2.70 (2.83), Zn 4.08 (4.17), W
58.34 (58.08), P 0.97 (1.02), K 6.69 (6.86).
Synthesis of K11[Lu{PZn2W10O38(H2O)2}2]·22H2O (Lu-11a)
Synthesis of K11[Dy{PZn2W10O38(H2O)2}2]·23H2O (Dy-6a)
Compound Lu-11a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.036 g Lu(NO3)3·H2O (0.1 mmol)
instead of Nd(NO3)3·6H2O. Colorless needle-shaped crystals were
obtained after about a few hours. Yield: 0.205 g (36%) (based on
K14[P2W19O69(H2O)]·24H2O). The numbers of crystal water molecules
have been determined by thermogravimetric analysis. FT-IR (with KBr
pellets): 1078(s), 1054(s), 1038(s), 946(s), 890(s), 812(s), 760(m), 692(m),
Compound Dy-6a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.044 g Dy(NO3)3·H2O (0.1 mmol)
instead of Nd(NO3)3·6H2O. Colorless needle-shaped crystals were
obtained after about a few hours. Yield: 0.311 g (55%) (based on
K14[P2W19O69(H2O)]·24H2O). The numbers of crystal water molecules
have been determined by thermogravimetric analysis. FT-IR (with KBr
pellets): 1075(s), 1054(s), 1036(s), 946(s), 891(s), 813(s), 756(m), 691(m),
627(w), 488(m), 430(w) cm–1
.
Elemental analysis (%) for
K11LuZn4P2W20O102H52; calcd. (found): Lu 2.78 (2.85), Zn 4.16 (4.21), W
58.47 (57.97), P 0.98 (1.01), K 6.82 (6.89).
618(w), 486(m), 426(w) cm–1
.
Elemental analysis (%) for
K11DyZn4P2W20O103H54; calcd. (found): Dy 2.55 (2.63), Zn 4.11 (4.52), W
57.75 (57.21), P 0.97 (1.10), K 6.74 (6.99).
Single-crystal structure determination
Synthesis of K11[Ho{PZn2W10O38(H2O)2}2]·23H2O (Ho-7a)
Single crystal structure data collection were performed on an Xcalibur
Oxford diffractometer, operated at 50 kV and 40 mA (Mo-K radiation, λ =
0.71073 Å, graphite monochromated).41 Pre-experiment, data collection,
data reduction were performed with the Oxford program suite
CrysAlisPro.42 The structures were solved by direct methods using
SHELXS-2008,43 which readily revealed the heavy atom positions (Ln and
W) and enabled us to locate the other non-hydrogen (K, P, and O)
positions from the difference fourier maps. An empirical absorption
correction based on symmetry-equivalent reflections was applied using
SCALE3 ABSPACK.44 The last cycles of refinement included atomic
positions, anisotropic thermal parameters for all the non-hydrogen atoms,
and isotropic thermal parameters for all the hydrogen atoms. Full-matrix
least-squares structure refinement against F2 was carried out using the
SHELXL-201543 package of programs. The Rint values for the crystal
structure of Sm-2a, Tm-9a, Yb-10a and Lu-11a are relatively higher due
to the poor crystal quality. Some of the structures contain the solvent
accessible voids as most of the oxygen atoms are disordered water
molecules. This has been removed by Platon SQUEEZE. Further details
on the crystal structure data may be obtained from the
Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen,
Germany (fax: (+49) 7247-808-666; e-mail: crysdata@fiz-karlsruhe.de),
on quoting the depository number CSD - 1905309 for compound Nd-1a,
CSD - 1905310 for compound Sm-2a, CSD - 1905311 for compound Eu-
3a, CSD - 1905312 for compound Gd-4a, CSD - 1905313 for compound
Tb-5a, CSD - 1905314 for compound Dy-6a, CSD – 1905315 for
compound Ho-7a, CSD - 1905316 for compound Er-8a, CSD - 1905317
for compound Tm-9a, CSD - 1905318 for compound Yb-10a and CSD -
1905319 for compound Lu-11a.
Compound Ho-7a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.044 g Ho(NO3)3·5H2O (0.1
mmol) instead of Nd(NO3)3·6H2O. Light yellow color needle-shaped
crystals were obtained after about a few hours. Yield: 0.307 g (54%)
(based on K14[P2W19O69(H2O)]∙24H2O). The numbers of crystal water
molecules have been determined by thermogravimetric analysis. FT-IR
(with KBr pellets): 1076(s), 1052(s), 1036(s), 946(s), 888(s), 813(s),
761(m), 688(m), 616(w), 486(m), 431(w) cm–1. Elemental analysis (%) for
K11HoZn4P2W20O103H54; calcd. (found): Ho 2.60 (2.51), Zn 4.13 (4.17), W
58.06 (57.85), P 0.98 (1.03), K 6.77 (6.60).
Synthesis of K11[Er{PZn2W10O38(H2O)2}2]·23H2O (Er-8a)
Compound Er-8a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.044 g Er(NO3)3·5H2O (0.1
mmol) instead of Nd(NO3)3·6H2O. Light pink color needle-shaped crystals
were obtained after about a few hours. Yield: 0.287 g (51%) (based on
K14[P2W19O69(H2O)]·24H2O). The numbers of crystal water molecules
have been determined by thermogravimetric analysis. FT-IR (with KBr
pellets): 1076(s), 1052(s), 1036(s), 946(s), 890(s), 814(s), 760(m), 694(m),
620(w), 486(m), 436(w) cm–1
.
Elemental analysis (%) for
K11ErZn4P2W20O103H54; calcd. (found): Er 2.65 (2.58), Zn 4.14 (4.23), W
58.20 (57.93), P 0.98 (1.07), K 6.79 (6.85).
Synthesis of K11[Tm{PZn2W10O38(H2O)2}2]·23H2O (Tm-9a)
Compound Tm-9a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.045 g Tm(NO3)3·5H2O (0.1
mmol) instead of Nd(NO3)3·6H2O. Colorless needle-shaped crystals were
obtained after about a few hours. Yield: 0.261 g (46%) (based on
K14[P2W19O69(H2O)]·24H2O). The numbers of crystal water molecules
have been determined by thermogravimetric analysis. FT-IR (with KBr
pellets): 1076(s), 1054(s), 1036(s), 946(s), 892(s), 812(s), 758(m), 698(m),
Thermogravimetric Analysis
In order to determine the number of crystal water molecules in the
compounds 1a–11a, thermogravimetric analysis was performed in the
temperature range of 25 – 600 °C with 5 °C/min heating rate under nitrogen
flowing atmosphere. A two-step weight loss is observed for all the
compounds in the temperature range of 25 – 350 °C. The weight loss was
associated with the loss of crystal water molecules (lattice and coordinated
water molecules). The total weight loss 8.19% for Nd-1a, 8.12% for Sm-
2a, 8.06% for Eu-3a, 8.17% for Gd-4a, 7.02% for Tb-5a, 8.17% for Dy-6a,
8.02% for Ho-7a, 8.04% for Er-8a, 8.11% for Tm-9a, 8.18% for Yb-10a
and 7.28% for Lu-11a, are associated with the loss of 27, 27, 27, 27, 26,
27, 27, 27, 27, 27, and 26 crystal water molecules, respectively along with
4 coordinated water molecules each (Fig. S11).
626(w), 486(m), 426(w) cm–1
.
Elemental analysis (%) for
K11TmZn4P2W20O103H54; calcd. (found): Tm 2.70 (2.75), Zn 4.19 (4.23), W
58.86 (58.24), P 0.99 (1.06), K 6.87 (6.78).
Synthesis of K11[Yb{PZn2W10O38(H2O)2}2]·23H2O (Yb-10a)
Compound Yb-10a was synthesized by following the above synthetic
procedure described for Nd-1a by using 0.045 g Yb(NO3)3·5H2O (0.1
mmol) instead of Nd(NO3)3·6H2O. Colorless needle-shaped crystals were
obtained after about a few hours. Yield: 0.253 g (45%) (based on
K14[P2W19O69(H2O)]∙24H2O). The numbers of crystal water molecules
have been determined by thermogravimetric analysis. FT-IR (with KBr
10
This article is protected by copyright. All rights reserved.

10.1002/ejic.202100528
European Journal of Inorganic Chemistry
FULL PAPER
Costes, Angew. Chem. 2007, 119, 2909-2912; Angew. Chem. Int. Ed.,
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Acknowledgements
F.H. thanks University of Delhi, SERB project EMR/2016/002812
and Institution of Eminence project IoE/FRP/PCMS/2020/27 for
the financial support of this research work. We also thank
University Scientific Instrumentation Center (USIC) for providing
instrument facilities, IIT Bombay for ICP-AES. V.D. and I.K. thank
CSIR, New Delhi for fellowship. M.S. and S.N. thank Grants-in-
Aid for Scientific Research (Scientific Research “C” (grant no.
26420787) and “B” (grant no. 19H02799)) of the Ministry of
Education, Culture, Sports, and Science, Japan. We thank Ms. T.
Amimoto at the Natural Science Center for Basic Research and
Development (N-BARD), Hiroshima University for the
measurement of ESI-MS.
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Keywords: Catalysis • Photoluminescence • Polyoxometalates •
Single Molecule Magnets • Thioether oxidation
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10.1002/ejic.202100528
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Insert text for Table of Contents here. A series of heterometallic 3d-4f tungstophosphate nanoclusters have been synthesized of which
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