Inorganic Chemistry Communications 96 (2018) 69–72

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Inorganic Chemistry Communications

journal homepage: www.elsevier.com/locate/inoche

Short communication

A new inorganic-organic hybrid transition-metal-substituted T

polyoxometalate
⁎
Min Cheng, Zhong Zhang, Hai-Lou Li, Guo-Yu Yang
MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China

G R A P H I C A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: A new inorganic-organic hybrid transition-metal-substituted polyoxometalate H27Na2[Co(en)3]2[{Co4(OH)3

Hydrothermal synthesis (PO4)}4(GeW9O34)4]·Cl·57H2O (1, en = ethylenediamine) was obtained under hydrothermal conditions and
Transition-metal-substituted polyoxometalates characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, elemental ana-
Inorganic-organic hybrid lysis, diffuse-reflectance spectroscopy and powder X-ray diffraction, respectively. Single-crystal structure ana-
lysis proved that polyanion [{Co4(OH)3(PO4)}4(GeW9O34)4]32− (1a) and complex cation [Co(en)3]2+ (1b) exist
in compound 1 simultaneously, exhibiting a 1D-chain built by 1a cluster units and Na+ cations. The cyclic
voltammetry (CV) shows reversible multielectron waves from the redox of WVI in 1.

It is well-known that transition-metal-substituted polyoxometalates tungstophosphates is {[FeII1.5FeIII

(TMSPs) are of great interest in the last decades owing to their con-
trolled structures. The physical and chemical properties of different
structures are applicable to diverse areas, such as magnetism, optics,
catalysis, sensor, luminescence and materials science [1–3].
TMSPs with different nuclearities have been explored energetically,
high-nuclearity TMSPs are usually made by bridge O/OH to assemble
into cluster [4–8], meanwhile the cluster skeleton becomes unstable
because of the growing degree of polymerization. So in order to make
and stabilize high-nuclearity TMSPs, small inorganic ligands (C2O42−,
CO32−, PO43−) [9–11] or organic ligands (en, piperazine, 1,2-diami-
nopropane) [12–14] have been widely employed.
As an inorganic ligand, PO43−, with abundant coordination sites,
small spatial steric resistance and abundant raw materials, it has been
widely used in making high-nuclearity clusters. The first PO43− ligand
used in tetrameric comprising 3d metal-containing Keggin
12(OH)12(PO4)4](B-α-PW9O34)4} in 2007
[15]. The first Co-containing similar structure with single molecule
magnet behavior [{Co4(OH)3PO4}4(PW9O34)4]28− was made in 2011
[16]. After that, [{Co4(OH)3PO4}4(XW9O34)4]n− (X = P, Ge, Si, As) was
produced in 2014 [17]. The above mentioned TMSPs all have a same
feature, a cubane unit {M4O4} (M = Co, Mn, Ni) locate the core of high-
nuclearity TMSPs. Up to date, besides the usual cubane unit, there are
some distorted cubane units such as quasi-cubane {MnIII IV
3 Mn O3} [18],
double-quasi-cubane {Co7O6} [19], face-sharing-double-cubane
{MnIII II
4 Mn2 O6} [20] and so on.
Our group has made great progress in TMSPs under hydrothermal
conditions [1,13–15,20]. As our continued work, herein a new in-
organic-organic hybrid TMSP, H27Na2[Co(en)3]2[{Co4(OH)3(PO4)}4
(GeW9O34)4]·Cl·57H2O (1) has been made. Compared to other similar
TMSPs, it has three traits: (1) By means of hydrothermal technique,
organic amines are introduced; (2) Inorganic ligand PO43− and organic

⁎
Corresponding author.
E-mail address: ygy@bit.edu.cn (G.-Y. Yang).

https://doi.org/10.1016/j.inoche.2018.08.002
Received 17 July 2018; Received in revised form 30 July 2018; Accepted 3 August 2018
Available online 04 August 2018
1387-7003/ © 2018 Elsevier B.V. All rights reserved.
M. Cheng et al.
ligand en exist in 1 simultaneously; (3) There are two kinds of OeNaeO
linkages to connect polyoxoanion form a 1-D chain.
Compound 1 was hydrothermally synthesized by the reaction of
Na10[A-α-GeW9O34]·18H2O (0.600 g, 0.21 mmol), Co(NO3)2·4H2O
(0.365 g, 2 mmol), Na3PO4·12H2O (0.380 g, 1 mmol) in a 25 mL Teflon-
lined autoclave with 8 mL distilled water. Adding 0.05 ml en to the
stirring mixture, pH get to 9 with 4 M HCl. The stirring continued for
30 min at room temperature, then the resulting mixture was sealed and
heated at 140 °C. After 3 days, cooled to room temperature, purple strip
crystals were obtained by filtration. Then washed with distilled water
and air-dried. Yield: 47% based on Na10[A-α-GeW9O34]·18H2O.
Elemental analysis calcd (wt%) for 1: C 1.17, H 1.65, N 1.37; Found: C
1.09, H 1.69, N 1.31. The phase purity of the products of 1 were proved
by the powder X-ray diffraction. The experimental pattern is in good
agreement with the simulated patterns from single crystal X-ray dif-
fraction (Fig. S1).
Single-crystal X-ray diffraction reveals that 1 crystallizes in the
monoclinic space group P21/c [21]. In the structure, the polyoxoanion
[{Co4(OH)3(PO4)}4(GeW9O34)4]32− (1a) contains 4 [GeW9O34]10−
fragments, 1 {Co16(OH)12} cluster, 4 PO43− groups, 2 [Co(en)3]2+
complex cations, 2 Na+, 1 Cl−, 27 protons and 57 lattice water mole-
cules (Fig. S2). The formation of the polyoxoanion 1a (Fig. 1d) can be
understood as follows: (1) Firstly, 4 Co2+ ions connect each other by
3 μ3-OH groups to form a Co4(OH)3 cluster and then capped on the
trilacunary precursor [A-α-GeW9O34]10− (Fig. 1a) to form the Co4-
substituted cluster [{Co4(OH)3}(GeW9O34)]5− (Fig. 1b). (2) Secondly,
four same [{Co4(OH)3}-(GeW9O34)]5− clusters are linked by 4 μ4-O
atoms to produce the cluster [{Co4(OH)3(μ4-O)}4(GeW9O34)4]28−
Fig. 1. (a–c) View of [A-α-GeW9O34]10−, [{Co4(OH)3}(GeW9O34)]5−, and [{Co4(OH)3(μ4-O)}4(GeW9O34)4]28−, respectively. (d) View of 1a. (e, f) View of {Co16O16}
unit and [Co(en)3]2+ cation. (g) View of the 1-D chain. Color codes: GeO4 yellow; WO6 red; CoO6 purple; Co4O4 light purple. (h) Simplified representation of 1-D
zigzag chain. 1a, red; OeNa1eO bond, dark green; OeNa2eO bond, light blue. (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)
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Inorganic Chemistry Communications 96 (2018) 69–72
(Fig. 1c). Notice that the precursor [A-α-GeW9O34]10− keep the same
conformation in the whole process of reaction. At last, four PO43− li-
gands shared μ4-O groups to further stabilize the cluster skeleton of 1a
(Fig. 1d), of which the distorted cubane {Co4O4} in the centre of
{Co16(OH)12O4} unit (Fig. 1e) consist of 4 μ4-O atoms and 4 Co2+ ions,
each [{Co4(OH)3}(GeW9O34)]5− cluster provide a Co2+ ion. As one of
type of counter cations, the complex [Co(en)3]2+ (1b, Fig. 1f) contains
three chelated en ligands and one Co2+ cation. In the asymmetric unit,
two [Co(en)3]2+ cations distribute on the both sides of the poly-
oxoanion 1a (Fig. S2). Interestingly, polyoxoanion 1a are linked by two
Na1+ and two Na2+ cations in two different directions to form a zigzag
1-D chain (Fig. 1g), and its simplified representation is shown in
Fig. 1h.
The oxidation states of all cobalt ions are +2 that have been proved
by BVS (bond valence sum calculations) (Table S1). There are three
crystallographically independent cobalt ions with hexa-coordination
modes in the asymmetric unit of 1: (1) the Co2+ ions occupied the
vacancy sites of precursor [A-α-GeW9O34]10− coordinate to 3 O atoms
of trilacunary precursor, a μ4-O (shared with PO4 ligand), 2 μ3-OH
groups; (2) the Co2+ ions of {Co4O4} cubane unit are coordinated by 3
μ3-OH groups and 3 μ4-O (shared with PO43− ligands); (3) the Co2+
ions of [Co(en)3]2+ complexes are completely different from fore-
mentioned, coordinate to 6 N atoms of 3 en ligands.
In the structure of 1, the CoeOeCo angles of cluster {Co16(OH)12}
are in the range of 91.4(7)°–133.3(9)°, which matches the range of the
CoeOeCo angles of 92.2(5)°–131.2(10)° in the reported Co16-cluster-
substituted POM [{Co4(OH)3(PO4)}4(PW9O34)4]28− [16]. According to
the structure and connection motif of magnetic centers in 1, possibly
M. Cheng et al.
Fig. 2. Cyclic voltammograms of 1-CPE in 1.0 M sulfuric acid aqueous solutions
with different scan rates (from inner to outer: 30, 50, 100, 150, 200, 250, and
300 mV s−1). (inset) Evolution of the first anodic peak current as a function of
the scan rate.
predict that ferromagnetic coupling between 16 Co2+ ions and can
behave as single-molecule magnets [16].
To investigate the electrochemical properties of 1, an experiment
which adopted CV method has been carried out, a carbon paste elec-
trode were used in the range of −1.0 V–1.0 V with different scan rates.
As shown in Fig. 2, there are two pairs of redox peaks, −0.439 and
−0.232 V (I, I′), −0.483 and −0.597 V (II, II′). In the scan rate of
300 mV s−1, mean peak potentials are calculated through the formula
E1/2 = (Epc + Epa)/2, −0.336 V (I–I′) and −0.570 V (II–II') which can
be attributed to the redox of W6+ atoms [22]. And the scan rates are
linearly related to the peak currents of the second anodic wave in
−1.0–1.0 V, proving that it is a surface-controlled process.
The FT-IR spectrum of 1 was recorded in the range of
4000–400 cm−1 (Fig. S3). The absorbtion bands 868, 929, 813, and
669 cm−1 belong to υGe-Oa (Oa: μ4-O), υW–Ot (Ot: terminal O atoms),
υW–Ob (Ob: μ2-O) and υW–Oc (Oc: μ3-O), respectively [23]. Besides that,
the bending vibration bands of eNH2 and eCH2 were discovered at
1626 and 1462 cm−1 respectively. The obvious absorbtion peaks at
3415 cm−1 is the characteristic peaks which indicate that the existence
of lattice water molecules. In a word, the IR spectrum proved the ac-
curacy of the structure ulteriorly.
Thermogravimetric analysis has been experimented at air atmo-
sphere from 25 to 1000 °C with a heating rate of 10 °C min−1 (Fig. S4).
It only went through one continuous weight loss step. From 25 to
591 °C, a weight of 14.37% should be assigned to the loss of 57 lattice
water molecules, a HCl molecule, 6 en ligands and dehydration of 12
hydroxyl groups and 26 protons, which is approximately matched with
the theoretical value (calcd.14.50%).
The optical properties of compound 1 was analyzed by changing
diffuse-reflectance spectroscopy obtained through Kubelka-Munk to
optical absorption spectrum with function: F(R) = (1-R)2/2R = α/S (R
is reflectance, α is absorbtion, S is scattering) [24,25]. Then make a
tangent to the curve through Eg axis, and intersection point shows that
1 has a band gap of 3.23 eV (1 eV < Eg < 4 eV), indicating 1 pos-
sesses semiconductor property (Fig. S5).
In a word, a new inorganic-organic hybrid Co16-cluster-substituted
POM has been made by hydrothermal technique and detailed char-
acterized, in which the PO43− inorganic ligands act as not only the
connector to form polynuclearity TMSPs, but also the stabilizer to sta-
bilize the polynuclearity cluster skeleton. Further work for making
high-nuclearity TMSPs by PO43− groups or other inorganic ligands is on
progress in our group.
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Inorganic Chemistry Communications 96 (2018) 69–72
Acknowledgements
This work was supported by the NSFC (nos. 91122028 and
50872133) and the NSFC for Distinguished Young Scholars (no.
20725101).
Appendix B. Supplementary material
CCDC 1854898 contains the supplementary crystallographic data
for 1. These data can be obtained free of charge via www.ccdc.cam.ac.
uk/conts/retrieving.html (or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)1223-336-
033; or e-mail: deposit@ccdc.cam.ac.uk). Supplementary data asso-
ciated with this article can be found in the online version at https://doi.
org/10.1016/j.inoche.2018.08.002.
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Inorganic Chemistry Communications 96 (2018) 69–72
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