Introducing chirality into hybrid clusters from an achiral ligand: Synthesis and characterization of polyoxomolybdates containing a benzylarsonate group

Article abstract of DOI:10.1002/ejic.201700265

Benzylarsonic acid as a flotation collector was introduced into polyoxometalate chemistry and two new hybrid clusters, [(C₆H₅CH₂AsO₃)₂Mo₅O₁₅]^4-(1and [(C₆H₅CH₂AsO₃)₄-Mo₁₂O₃₄]^4-(2a), were synthesized and characterized by chemical and spectral analysis. Self-assembly of 1a led to chiral crys-tals of compound 1, whereas compound 2 was found to be a racemic mixture of the “inverted-Keggin” hybrid cluster of 2a. Both compounds were charactsned.

Full text of DOI:10.1002/ejic.201700265

A Journal of
Accepted Article
Title: Introducing Chirality Into Hybrid Clusters From Achiral Ligand:
Synthesis and Characterization of Polyoxomolybdates Containing
Benzyl Arsonate Group
Authors: Meng-Shu Liu, Wei-Dong Yu, Qian-Wen Yan, and Jun Yan
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700265
Link to VoR: http://dx.doi.org/10.1002/ejic.201700265

European Journal of Inorganic Chemistry
10.1002/ejic.201700265
COMMUNICATION
Introducing Chirality Into Hybrid Clusters From Achiral Ligand:
Synthesis and Characterization of Polyoxomolybdates Containing
Benzyl Arsonate Group
[
a]
[a]
[a]
[a]
Meng-Shu Liu, Wei-Dong Yu, Qian-Wen Yan, and Jun Yan*
Abstract: The benzyl arsenic acid flotation collector is introduced
2 4 3 6 5 2 3 4 2
9H O (1) and (NH ) Na-[(C H CH AsO ) Mo12O34] · 14H O (2)
into polyoxometalate chemistry and two new hybrid clusters,
respectively. Unexpectedly, insertion of this achiral ligand results
in the chirality of both compounds, and crystal of 1 is a single
enantiomer constructed by achiral cluster 1a, while compound 2
is racemic mixture. Both of the compounds were characterized,
as well as their redox properties were primarily examined.
4-
4-
[
6 5 2 3 2 5 15 6 5 2 3 4 34
(C H CH AsO ) Mo O ] (1a) and [(C H CH AsO ) Mo12O ] (2a),
have been synthesized and characterized by chemical and spectral
analysis. Self-assembly of 1a leads to chiral crystals of compound 1,
while compound 2 presents racemic mixture of “Inverted-Keggin”
hybrid cluster of 2a. Both of the compounds were characterized in
solid state, as well as their redox properties were primarily examined.
Results and Discussion
Introduction
The solid benzyl arsonic acid was synthesized using the classic
method with yield of 85%, as shown in Scheme 1. Compound
[
17]
Flotation is a cost-effective mineral processing method and
widely used to beneficiate heavy metal containing minerals such
as wolframite slime. Collectors such as organophosphate and
organoarsonate derivatives play an important role in obtaining
1 was synthesized by directly mixing of (NH ) Mo O ·4H O,
4
6
7
24
2
ammonia and benzyl arsonic acid in an orderly manner, and
then the pH of the solution was adjusted to about 4.5 by
hydrochloride acid. Evaporation of the solution leads to the
[
1]
enriched product with satisfactory grade and recovery. Therefore, forming of crystals suiting for single crystal X-ray diffraction of 1
understanding the flotation chemistry between organic collectors
in a day. Compound 2 was isolated in a similar procedure but
the pH was adjusted to 1.0. Like the synthesis of other
organoarsonate hybrid, benzyl arsonic acid is easy to embed
and oxometallate in solution could benefit the design and choice
[
2]
of collectors. Generally, the coordination between such acid
type collector and early transition metallates results in the
modification of organic derivatives of polyoxometalate (POM)
[
8-9]
into POM framework at acidic condition.
The pH scanning in
the synthesis shows that only 1a cluster can be isolated under
weak acidic condition between pH 3~6, and no other clusters
has been detected yet. When the pH of the solution is below 2,
additional photo-redox processes of molybdate species was
observed during the synthesis. Though the redox process of Mo
fragment is complicated and the role is uncertain in forming of
cluster 2a, the nattier blue crystals of compound 2 could be
isolated in the dark blue solution with all the Mo centers fully
oxidized at the pH range of 0.5~2.5.
[3-4]
and their structures by varying synthetic parameters.
These
multifunctional covalently bonded hybrid POM architectures
have received great interest and expanded largely during the
[
5-8]
last decade.
A few types of hybrid POM structures with
different functional organoarsonate group have been reported,
4
-
examples majorly including {Mo
CH CH CH CH CH CH CH CH
AsR) } , and {Mo12
, C -4-NH
, C -4-CN, C
5
O
15(O
3
AsR)
2
}
3
(R=CH ,
[9]
4-
2
3
,
2
2
3
,
2
2
2
),
{Mo
4
4-
O
10(O
3
AsR)
(R=C
-4-OH-
It is noticed that
4
} ,
H ,
6 5
4
-
{
C
3
Mo
6
O
18(O
3
2
O
34(O
3
AsR)
4
}
6
H
-NO
4
CH
3
6
H
4
2
, C
6
H
4
-4-OH, C
-4-OH-3-NOC
6
H
4
-4-COOH, C
6
H
3
Single crystal X-ray diffraction analysis reveals that the 1a is
[10-16]
[9]
2
6
H
4
6
H
3
2
H
4
).
a classical Strandberg-Type molybdates. As shown in Fig. 1,
the commercially use of efficient collector benzyl arsonic acid in
flotation have not studied in polyoxometalates yet and it is
promising in forming such hybrid compounds by the introduction
of benzyl group to coordinate both the structures and properties
towards functional complex material. In this regards, the self-
assembly behavior of benzyl arsonic acid with molybdates in
aqueous solution is studied. Two new hybrid POM clusters
all the five Mo centers are six coordinated and linked two
terminal O ligand with average Mo=O bond length of 1.71(1)Å.
These metallate octahedra link to a {Mo O } ring by sharing O
5
21
ligands. The organic benzyl arsenic group bonds to the ring by
forming three As-O-Mo bonds. To fit the cavity, the AsO group
3
is slightly compressed with the O-As-O bond angle of 110.18(1)°,
107.90(1)° and 105.04(1)°. The interfacial angle of As-CH2-
4
-
containing benzyl arsonate, namely [(C
6
H
5
CH
(2a), have been
5
CH AsO Mo O15] ·
2 3 2 5 15
AsO ) Mo O ]
4
-
(
1a) and [(C
6 5 2 3 4 34
H CH AsO ) Mo12O ]
synthesized and isolated as (NH
4
)
4
[(C
6
H
5
2
3
)
2
[
a] School of Chemistry and Chemical Engineering, Central South
University,
Changsha 410083, P.R. China
E-mail: yanjun@csu.edu.cn
Scheme 1. Synthetic process of the benzyl arsonic acid.
Supporting information for this article is given via a link at the end of
the document.
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European Journal of Inorganic Chemistry
10.1002/ejic.201700265
COMMUNICATION
Figure 1. Ball-and-stick representations of the hybrid cluster 1a (left) and 2a
Figure 2. Left: Polyhedron representations of {(Mo
in 1 (the {MoO } unit are shown in green, the {CAsO
and the central cavity is shown in perspective mode); Right: the solid-state
circular dichroism spectrum of 1.
5
As
2
)
6
} Supra-molecular ball
3
} are shown in orange
(right) containing benzyl arsonate unit. (Color code: O, red; Mo, Green; As,
6
Orange; C, black; H, gray)
phenyl bond is 88.92(5)°, and two organic ligands are oriented
like two wings and located at the side of the metal oxide units.
The additional methylene group allows phenyl group slightly
rotate and therefore increase of clusters’ flexibility and decrease
the symmetry of the 1a cluster, which result that its ammonium
salt crystallized in a chiral space group of F23. Both Multiple
Single crystal X-ray diffraction test and polarizing microscope
view of the compound confirmed that no other enantiomer was
detected and compound 1 is enantiopure. This phenomenon is
rare, as the introduction of chirality to achiral building units
always goes in two ways; either the system needs additional
chiral source or the enantiomer clusters crystallized via
[
9]
via the disorder of the organic chain during the crystallization.
The solid natures of the two compounds were inspected
chemically. The phase purity of the compounds was examined
by Powder-XRD. The experimental data has shown good
agreement with simulated patterns of 1. Some difference was
detected in the case of 2, which may caused by the lattice water
loss of the crystal and moisture absorption of the Ammonium ion
in the measurement. The diffraction peaks on the patterns
correspond well in position, confirming that the product is in a
pure phase. The differences in reflection intensity are probably
due to the preferred orientation in the powder samples. The
solvents are further determined by combining TGA-DSC and
Single crystal diffraction data. The solid UV-Vis absorption
spectra shows very weak absorption for 1 and no absorption for
2 in the visible region, which indicates that all Mo centers in both
the clusters are fully oxidized. As expected, the solid-state
circular dichroism (CD) data shows that compound 1 exhibits
[
18-23]
spontaneous resolution that needs sorted manually.
So far,
only one example of direct synthesis of single enantiopure
hybrid POM is reported, which also belongs to the Strandberg-
Type hybrids cluster containing adenosine-5-monophosphoric
[
19]
acid ligand.
together by H-Bond and formed a half-closed supra-molecular
chiral octahedral {(Mo As } secondary building unit in solid
As shown in Fig. 2, six 1a clusters are linked
5
2 6
)
structure. The closed four faces of the octahedral unit are
constructed by phenyl groups and the open faces and inside
space of the unit are filled by the cations and solvent water,
which is curial to stabilize the component and maintain the
chirality.
4
-
In contrast, cluster 2a [(C
6 5 2 3 4 34
H CH AsO ) Mo12O ] reveals a
classic “inverse-Keggin” cluster, where the tetrahedral {RAsO
3
}
[
24-26]
units are located on the surface of the cluster.
The main
body of the cluster is nearly identical to the reported analogous
[
15]
with the exception of the organic group. The hybrid cluster is
also -4 charged and the organic group is neutral. As shown in
Fig. S21, the clusters is intrinsically chiral due to the rotation of
phenyl group. But it only results in the optically inactive racemic
mixture of the enantiomeric chiral crystals in the space group of
+
P
21/n in aqueous solution. One Na is detected in the structure,
which attaches on the cluster by making two Na-O=Mo bonds
and links another four water molecules to form the secondary
building units, and then further packing to 3D supra-molecular
network. As noticed, the size and the weak rigidity of the ligands
are crucial in chiral hybrid crystal generation. Replacing benzyl
arsonate with benzyl phosphate in the synthesis produces only
[27]
Figure 3. Top: The H-NMR spectrum of compound 2 in D
part of cluster is simplified as a ball and the three type of H at benzyl arsenite
are marked in order (* signal come from the residual solvent H O); Bottom:
The negative mode ESI-MS of 2 in CH CN.
2
O, the inorganic
symmetric Strandberg-Type cluster.
Also, most of reported
hybrid cluster containing flexible organic arsonate can yield
chiral cluster while they always form enantiomeric compounds
2
3
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European Journal of Inorganic Chemistry
10.1002/ejic.201700265
COMMUNICATION
+
strong positive Cotton effect at 323 nm and opposite cotton
effect at 289nm and several weak Cotton effect is also detected
in the range of 200-300 nm. While compound 2 is CD-silent,
confirming that compound 1 show bulk chirality in the solid state,
and 2 crystallizes as a racemic conglomerate (See Fig. 2 and
S21).
wave slightly shifts to -0.85V (vs. Ag/Ag ), which may
contributed to benzyl arsonate group because no “molybdate
blue” spieces was detected. But an extra quasi revisable redox
couple was clearly detected at E1/2 = -1.23V can be assigned to
VI
V
Mo /Mo
redox
reactions
combining
with
protonation/deprotonation process since benzyl arsonic acid is
The solution behaviors of these clusters also have been
no redox active, which indicates cluster 2a could be a good
studied. The H-NMR study of 1 in D
2
O shows that the compound
precursor
in
constructing
new
redox
active
is not stable in aqueous solution and cluster dissociation is
detected. The methylene H signal appears at 3.85 in benzyl
arsonic acid reactant and shifts to 4.57 after it forms cluster 1a,
while the signal of aromatic H still locates in the classic zone
between 7~8 ppm. The methylene H signal strongly shift
because the deprotonation of adjacent arsonate group and their
coordination to the polyanion which has abundant electron.
However, three more single peaks at 4.08, 3.92 and 3.50 are
detected, which belong to the decomposed fragments. The
negative mode ESI-MS data also confirms this process. Not only
heteropolyoxomolybdates.
Conclusions
In conclusion, two new molybdo-benzylarsonate hybrid clusters
were isolated and characterized by chemical and spectral
analysis. Benzyl arsonate group was embedded in the
polyoxometalate framework for the first time and adjusting of the
flexibility of organic group significantly tune the assembly
process of the hybrid compounds, as well as the redox
properties. Compound 1 shows the second POM example with
spontaneous resolution self-assembly process leading single
enantiopure crystals with achiral cluster, while Inverted-Keggin
type hybrid compounds compound 2 could be potential redox
active precursor in further functional molecule design. The
further study on the coordination behavior with other early
transition metals and redox intermolecular reassembly of the
clusters are now in progress, and the results will be reported in
due time.
2
-
the molecule ion peak of {H(NH
79.17 and {(NH [Mo
4
)[Mo
AsO
5
O
15(C
7
H
7
AsO
3 2
) ]} at m/z
2
-
5
4
)
2
5
O
15(C
7
H
7
3 2
) ]} at m/z 590.81 were
spotted, but also a serious fragment peaks containing benzyl
arsenic group could be assigned with general formula of
{
(
(MoO
3 a 7 7 3 b C
) (C H AsO ) H } (a = 1,2,3 or 4; b =0, 1 or 2; c = 0 or 1)
See Supporting Information). The cluster 2a is steadier in
solution. As shown in Fig. 3, the H-NMR shows clear signals of
three type of H from the hybrid cluster at 4.56, 7.11 and 7.64
with ratio of 2:3:2, which can be clearly assigned from the cluster.
Also the ESI-MS in acetonitrile of 2a shows two main peaks
2
-
which can be assigned as {H
2
Mo12
O
34(C
6
H
5
3
CH
2
AsO
3
)
4
}
(m/z
-
1276.46) and {HMo12O34(C H CH AsO ) }
6 5 2 3 4
(m/z 851.32).
Additionally, a supramolecular dimer peak of 2a was identified at
m/z 1721.93.
Experimental Section
Further, the redox behaviors of the clusters were preliminary
investigated by cyclic voltammetry and differential pulse
voltammetry. Both of the clusters have two cis terminal oxygen
in a molybdenum unit and should not have redox active in
Synthesis of benzyl arsonic acid: Na
was dissolved in 30mL deionized water under stirring at room
temperature. Then C CH Cl (3.9mL, 30.02mmol) was added
3 3
AsO (3.9g, 30.02mmol)
[28]
accordance with Pope’s rule (type II).
Cluster 1a fits the rule
6
H
5
2
well and only an irreversible reduction wave appears at -0.90V
to the solution. The mixed solution was stirring 5h at 75℃.
Remove the superior benzyl alcohol and reserve the lower
solution. In the stirring, dilute sulfuric acid was added slowly to
control the pH between 2 and 3. Then, white solid was
precipitated and collected. Yield: 5.5g (85% based on As). ESI-
(
vs. Ag/AgCl) in acidic buffer solution at 100mv/s scanning rate,
15b
which is consistent with the other previous report.
However,
cluster 2a shows rich redox properties in CH
shown in Fig. 4, the irreversible
3
CN solution. As
reduction
-1
MS: m/z 214. 96. IR (KBr, cm ): 3463(br), 2734(br), 2308(br),
1
6
496(m), 1455(m), 1189(m), 1122(m), 1070(w), 890(s), 779(s),
90(s), 466(m).
4 6 7 2
Synthesis of compound 1: (NH ) Mo O24•4H O (10g, 8.1mmol)
was dissolved in 60 mL deionized water under stirring at room
temperature. Then ammonia (25%, 3.36mL, 45mmol) was
added to the above solution. After stirring 10 min, benzyl arsonic
acid (5.7477g, 26.6mmol) was added. The pH of the mixture
-1
was adjusted to 4.7 with 6 mol•L HCl and then heated to 100℃
until the volume was reduced to 40-45 mL. The slightly turbid
was filtered after standing to cool to room temperature and the
filtrate was evaporated in the air. After 1d, pale yellow block
crystals of 1 were formed. Yield: 2.78g (39.4% based on Mo).
Elemental analysis (%) calc. for C14
48 4 2 5
H N As Mo O30: C, 12.17; H,
3.50; N, 4.05; Mo, 34.7% found: C, 12.4; H, 3.8; N, 4.2; Mo,
-
2
Figure 4. Cyclic voltammogram of compound 2 (1 × 10 M) in CH
containing 0.1mM/L TBABF at scan rate 100 mV/s.
3
CN
4
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European Journal of Inorganic Chemistry
10.1002/ejic.201700265
COMMUNICATION
-1
3
1
5.51%. IR (KBr, cm ): 3415(s, br), 3120(s, br), 1630(m),
491(m), 1400(s), 1064(w), 897(s), 829(s), 672(s), 488(s).
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1
3.3mmol) was added. The pH of the mixture was adjusted to
-1
1.0 with 6 mol•L HCl. Then NaCl (0.067g, 1.14mmol) was
added and the mixed solution was heated to 100℃ for 30 min.
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.46%. IR (KBr, cm ): 3482(s, br), 3169(s, br), 1634(m),
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This work was supported by the National Science Foundation of
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European Journal of Inorganic Chemistry
10.1002/ejic.201700265
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Polyoxometalate hybrid*
Mengshu Liu, Weidong Yu, Qianwen
Yan, and Jun Yan*
1– 5
Introducing Chirality Into Hybrid
The benzyl arsenic acid is introduced into polyoxometalate chemistry and two
new chiral hybrid clusters have been synthesized and characterized.
Clusters From Achiral Ligand:
Synthesis and Characterization of
Polyoxomolybdates
Containing
Benzyl Arsonate Group
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