Lanthanide complexes of anthraquinone-1,8-disulfonate: Syntheses, structures and catalytic studies

Article abstract of DOI:10.1016/j.inoche.2021.108682

Two isostructural series of four lanthanide coordination complexes have been synthesized by hydrothermal method with anthraquinone-1,8-disulfonate as the anionic ligand. The complexes also comprise K⁺ ions that participate into coordination to

Full text of DOI:10.1016/j.inoche.2021.108682

Inorganic Chemistry Communications 130 (2021) 108682
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Short communication
Lanthanide complexes of anthraquinone-1,8-disulfonate: Syntheses,
structures and catalytic studies
,
,
,e,*
Fu-Yu Caoa, Meng-Ping Huanga, Hui-Lei Gaob, Xiao-Li Zhaoc *, Jie Hand *, Xu-Dong Chena
a Jiangsu Collaborative Innovation Center of Biomedical Functional Materials and Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials
Science, Nanjing Normal University, Nanjing 210023, Jiangsu, China
b Chemistry Group, Dongying Chenyang School, Dongying District, Dongying City 257000, Shandong Province, China
c Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, China
d School of Science & Technology, The Open University of Hong Kong, Kowloon, Hong Kong Special Administrative Region, China
e State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, Jiangsu, China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Two isostructural series of four lanthanide coordination complexes have been synthesized by hydrothermal
method with anthraquinone-1,8-disulfonate as the anionic ligand. The complexes also comprise K+ ions that
participate into coordination to form bimetallic complexes. The ligands in these complexes chelate to either
lanthanide or K+ ions, and in some circumstance bridge the ions as well. Besides inter-/intra- molecular hydrogen
Anthraquinone-1,8-disulfonate
Lanthanide coordination compounds
Catalysts
Oxidation
bonding between the sulfonate groups and water molecules, π-π stacking interactions also contribute to the
Sulfoxide
stabilization of the crystal packing. Investigation of the catalytic properties of the complexes indicated that they
were able to promote the oxidation reaction of thioethers into sulfoxides, in which the Er3+ coordination
complex exhibited the best catalytic efficiency over a wide range of substrates.
1. Introduction
This is because sulfonate group is “soft” in terms of coordination char-
acters and is less favorable by transition metal ions in forming coordi-
Lanthanide coordination polymers (Ln-CPs) constructed by lantha-
nide ions and organic ligands [1] have attracted a lot of research interest
because of their great promise for the development of materials with
potential applications in areas such as gas adsorption and separation
[2–5], tunable luminescence [6–11], proton conductivity [3,12],
chemical sensing [13–18], and catalysis [19–25]. These unique prop-
erties mainly arise from 4f electrons of the lanthanide ions or the organic
ligands, as well as the interactions between them that produce syner-
gistic effect [1,7,14]. Lanthanide ions have high and variable coordi-
nation numbers with flexible coordination geometry adaptive to
versatile frameworks [1].
nation complexes [32]. However, the sulfonate group coordinates with
lanthanide ions very well and its steric feature allows more structural
diversity [26,29]. On the other hand, the anthraquinone was selected for
modification because of the rich redox properties of quinone compounds
[33,34]. The redox processes of quinone compounds are commonly
accompanied by single electron transfer or proton coupled electron
transfer [35,36], dictating their potential applications in catalysis
[37–39]. This property might be transferable into their coordination
complexes and the catalytic efficiency might even be strengthened in
certain cases due to synergistic effect. Therefore, the lanthanide coor-
dination complexes of anthraquinone-1,8-disulfonate were synthesized
and characterized, and their catalytic properties were studied.
Since lanthanide ions have a strong coordination affinity for oxygen
[26], we utilized a sulfonate functionalized anthraquinone ligand for the
construction of novel lanthanide coordination polymers. Compared to
the widely used coordination group of carboxylate, sulfonate group are
less employed as the coordination group in organic ligands [27–31].
The oxidizing reaction of sulfides into sulfoxides was selected as the
substrate reaction. Sulfoxides are important industrial intermediates
[40], but the over oxidation of thioethers may result in the generation of
sulfones instead of sulfoxides [41,42]. Therefore, the controlled
* Corresponding authors at: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University,
Shanghai 200062, China (X.-L. Zhao); School of Science & Technology, The Open University of Hong Kong, Kowloon, Hong Kong Special Administrative Region,
China (J. Han); Jiangsu Collaborative Innovation Center of Biomedical Functional Materials and Jiangsu Key Laboratory of New Power Batteries, School of Chemistry
and Materials Science, Nanjing Normal University, Nanjing 210023, Jiangsu, China (X.-D. Chen).
E-mail addresses: xlzhao@chem.ecnu.edu.cn (X.-L. Zhao), chan@ouhk.edu.hk (J. Han), xdchen@njnu.edu.cn (X.-D. Chen).
https://doi.org/10.1016/j.inoche.2021.108682
Received 19 March 2021; Received in revised form 29 April 2021; Accepted 17 May 2021
Available online 20 May 2021
1387-7003/© 2021 Elsevier B.V. All rights reserved.

F.-Y. Cao et al.
Inorganic Chemistry Communications 130 (2021) 108682
oxidation of thioethers into sulfoxides has received extensive attention
in recent years [42,43]. Despite extensive research on the selective
oxidation of thioethers into sulfoxides, it is still of great importance to
develop efficient catalyst with good product selectivity.
SHELXL-2014 and OLEX2 program. All non-hydrogen atoms were
refined anisotropically. Non-water hydrogen atoms were added at
calculated positions and refined using a riding model. Hydrogen atoms
of water molecules were located by different Fourier map and refined
using riding model at restrained distance of 0.86 Å. Crystallographic
data for all complexes are summarized in Table 1.
2. Experimental section
2.1. General
3. Results and discussion
All reagents and solvents were purchased from commercial sources
and used without further purification. Thermal analyses were carried
out on a Mettler-Toledo TGA/DSC STARe system in the temperature
range of 28–800 ◦C with a heating rate of 10 ◦C⋅minꢀ 1, under nitrogen
flow. Infrared spectra were recorded on a VECTOR 22 spectrometer with
pressed KBr pellets in the range of 4000–400 cmꢀ 1. Powder X-ray
diffraction (PXRD) was done with a MiniFlex 600 X-ray powder
diffractometer equipped with a Cu sealed tube (λ = 1.54178 Å) at 40 KV
and 40 mA. 1H and 13C NMR spectra were obtained in CDCl3 solvent on a
Bruker 400 MHz spectrometer. Elemental analyses were performed
using a PE-240C elemental analyzer.
With
corresponding
lanthanide
salts
and
dipotassium
anthraquinone-1,8-disulfonate, four bimetallic coordination complexes
were synthesized using similar hydrothermal method, which include
{[LnK(AQDS)2(H2O)4]⋅3H2O}n (Ln = La (1) or Nd (2)) and {[LnK
(AQDS)2(H2O)8]n (Ln = Gd (3) or Er (4)). The isostructural complexes 1
and 2 crystallize in the monoclinic space group P21/n. Each asymmetric
unit comprises one Ln3+ cation, one K+ cation, two AQDS2ꢀ anions, four
coordinated water molecules and three lattice water molecules (Fig. 1a).
Detailed structural features will be discussed with complex 1 as an
example hereafter. The nine-coordinated K+ cation is surrounded by
four AQDS2- anions, binding with sulfonate O atoms and carbonyl
groups at distances between 2.656(6) to 3.266(5) Å. A couple of adja-
cent symmetry related K+ cations are chelated by two symmetry related
AQDS2ꢀ anions to form dimeric moiety with K⋅⋅⋅K separation of 4.095(6)
Å. These dimeric moieties are further bridged by sulfonate O atoms of
other symmetry related AQDS2ꢀ anions to constitute a column (Fig. 1b).
{[LnK(AQDS)2(H2O)4]⋅3H2O}n (Ln ¼ La (1) and Nd (2)). These
compounds were prepared by the same procedure as follows. A mixture
of lanthanide salt (La(NO3)3⋅6H2O (14.3 mg, 0.033 mmol) or
NdCl3⋅6H2O (11.8 mg, 0.033 mmol)) and K2AQDS (dipotassium
anthraquinone-1,8-disulfonate, 22.2 mg, 0.05 mmol) in 2 mL H2O was
placed in a 10 mL glass vial. After ultrasonic treatment for 20 min, the
It is interesting that π-π stacking interactions also exist within the col-
◦
sample was heated at 100 C for 12 h, and then cooled to room tem-
umn and the centroid-to-centroid distances are 3.808(7) and 3.835(6) Å,
which contribute to stabilizing the crystal packing (Fig. 1b). The coor-
dination sphere of the K+ cation is also complemented by a carbonyl O
atom from another AQDS2ꢀ anion that chelates to the La3+ cation. The
La3+ cation is also nine-coordinated. It is chelated on one end by an
AQDS2ꢀ anion through two sulfonate groups and the carbonyl group in-
between the sulfonate groups. On the other end, the La3+ cation is
chelated by two sulfonate groups of the dimeric [K-AQDS] moiety. The
coordination sphere of the La3+ cation is further complemented by four
aqua ligands. The La ꢀ O bond distances range from 2.508(5) to 2.683
(5) Å.
perature. The resulting pale yellow needle-like crystals were collected
by filtration, washed with methanol, and dried under vacuum. Yield:
78% for 1; 80% for 2. Elemental analysis for 1 (C28H26KLaO23S4), calcd
(%): C, 32.44; H, 2.53. Found: C, 32.69; H, 2.48. Elemental analysis for 2
(C28H26KNdO23S4), calcd (%): C, 32.27; H, 2.51. Found: C, 32.41; H,
2.55.
[LnK(AQDS)2(H2O)8]n (Ln ¼ Gd (3) and Er (4)). The synthesis is
similar as that for 1 and 2 except that Gd(NO3)3⋅6H2O (14.9 mg, 0.033
mmol) or ErCl3⋅6H2O (12.6 mg, 0.033 mmol) was used as the respective
lanthanide salt. Plate-shaped red-brown-colored crystals appropriate for
single-crystal X-ray diffractions were obtained. The crystals were sepa-
rated by filtration, washed with methanol, and dried under vacuum.
Yield: 72% for 3 and 78% for 4. Elemental analysis for 3 (C28H28Er-
KO24S4), calcd (%): C, 31.05; H, 2.61. Found: C, 30.94; H, 2.51.
Elemental analysis for 4 (C28H28GdKO24S4), calcd (%): C, 31.34; H, 2.63.
Found: C, 31.28; H, 2.59.
The two AQDS2ꢀ anions in the asymmetric unit take different coor-
dination modes. One of them chelates the La3+ cation through two
sulfonate groups and the carbonyl group in-between the sulfonate
groups, and the carbonyl group in the opposite side of the La3+ cation
bridges to the K+ cation. The other AQDS2ꢀ ligand chelates to a couple of
K+ cations with two sulfonate groups and the carbonyl group in-between
the sulfonate groups but the other carbonyl group has only hydrogen
bonding interactions instead of coordination. The chelation with metal
ions in both AQDS2ꢀ ligands leads to significant bending of the ligand,
resulted in that the carbonyl group in-between the sulfonate groups falls
out of the conjugation plane obviously. The dihedral angle between the
2.2. Typical procedure for oxidation of thioether
A mixture of catalyst (0.02 mmol) and thioether (0.4 mmol) in 2.0
mL methanol was added to a 25 mL Schlenk tube equipped with a
magnetic stir bar. After the addition of 30% hydrogen peroxide (1.2
mmol), the reaction mixture was stirred at room temperature for 24 h in
ambient air. Filtration was done after the reaction, and the filtrate was
extracted with water/ethyl acetate for three times. The combined
organic phase was dried over anhydrous Na2SO4, evaporated to dryness,
and then subjected to column chromatography (silica gel, ethyl acetate)
to afford pure sulfoxide product. The yields reported are based on the
–
–
C
C( O) C plane and the C14 plane is 27.3(5)/9.3(5) for the AQDS2ꢀ
–
–
ligand chelating to K+ cation and 13.7(5)/7.7(5) for the other one
binding with La3+ cation.
Isostructural complexes 3 and 4 crystallize in the monoclinic space
group C2/c and 4 will be used as an example for detailed structure
description. The asymmetry unit contains one Er3+ cation and one K+
cation, two AQDS2ꢀ ligands, eight aqua ligands (Fig. 1c). The twelve-
coordinated K+ ion is chelated by two symmetry related AQDS2ꢀ li-
gands and two aqua ligands to form a subunit. These K+ subunits were
bridged by [Er(H2O)6]3+ subunits through Er-sulfonate coordination,
generating 1-D chain structure. The 1-D chains are further linked
isolated pure product and characterization was performed by 1H and 13
NMR spectroscopy.
C
2.3. Single crystal X-ray crystallography
–
together by rich O H⋯O hydrogen bonding to afford a 2-D layered
structures, which further assemble into 3-D structure via stacking
interactions. The Er-O bond lengths range from 2.307(2) to 2.366(2) Å
Single crystal X-ray diffraction data of all complexes were collected
at 293 K on a Bruker APEX II CCD diffractometer operating at 50 KV and
π-π
–
and the K O bond distances fall in the range of 2.766(2)-3.324(3) Å.
30 mA using Mo K
α
radiation (λ = 0.71073 Å). Data were integrated by
SAINT and scaled with either a numerical or multi-scan absorption
correction using SADABS. All structures were solved by direct methods
or Patterson maps and refined by full-matrix least squares on F2 using
The centroid-to-centroid distances of the π-π stacking interactions are
3.634(2) and 3.822(19) Å (Fig. 1d). Similar as that in 1, the AQDS2ꢀ
ligand also bends significantly to facilitate its chelation with metal ions,
2

F.-Y. Cao et al.
Inorganic Chemistry Communications 130 (2021) 108682
Table 1
Crystallographic data of complexes 1–4.
1
2
3
4
Empirical formula
C
28H26KO23S4La
C28H26KNdO23S4
1042.07
monoclinic
P21/n
C28H28KO24S4Gd
C28H28KO24S4Er
1083.10
monoclinic
C2/c
Fw
1036.74
monoclinic
P21/n
1073.09
monoclinic
C2/c
Crystal system
Space group
a(Å)
7.435(13)
25.58(4)
19.02(3)
90
7.398(3)
25.308(8)
18.862(7)
90
7.7884(13)
23.650(4)
19.883(3)
90
7.7514(5)
23.8445(16)
19.6001(13)
90
b(Å)
c(Å)
α
(◦)
β(◦)
95.39(4)
90
95.449(5)
90
95.685(2)
90
96.383(2)
90
γ(◦)
V(Å3)
3602(10)
4
3516(2)
4
3644.4(10)
4
3600.2(4)
4
Z
ρcal(g⋅cmꢀ 3
)
1.912
1.969
1.956
1.998
μ
(mmꢀ 1
)
1.628
1.930
2.261
2.777
F(000)
2072.0
2084.0
2140
2156
Goodness-of-fit on F2
1.020
1.009
1.052
1.063
Ra1, wRb2 [I > 2
σ
(I)]
0.0448, 0.0708
0.0912, 0.0833
0.69/-0.75
0.0554, 0.0862
0.1173, 0.1052
1.44/-0.98
0.0304, 0.0706
0.0356, 0.0736
0.947/ ꢀ 0.616
0.0260, 0.0619
0.0308, 0.0635
0.521/-0.532
Ra1, wRb2 (all data)
(Δ
ρ
)max/(Δ
ρ
)min (e Åꢀ 3
)
Fig. 1. (a) The asymmetric unit in 1 showing coordination geometries of metal centers and binding modes of the ligands. Symmetry codes: i2-X,1-Y,1-Z; ii1 + X,+Y,+
Z; iii1/2 + X,3/2-Y,-1/2 + Z; iv-1/2 + X,3/2-Y,1/2 + Z. Lattice water omitted for clarity. (b) The
π ꢀ π stacking interactions in complex 1. (c) The asymmetric unit in 4
showing coordination geometries of metal centers and binding mode of the ligand. Symmetry codes: i-X,+Y,3/2-Z; ii1-X,1-Y,1-Z; iii-X,1-Y,1-Z; iv1 + X,+Y,+Z. (d) The
π
ꢀ π stacking interactions in complex 4.
3

F.-Y. Cao et al.
Inorganic Chemistry Communications 130 (2021) 108682
–
–
–
and the dihedral angle between the C C( O) C plane and the C14
catalytic system (Table 2). The results showed that electron-donating
substituents on the phenyl ring of aryl methyl sulfides facilitate the
oxidation reaction and result in high yield of 80% (6b, 6c), being
comparable with that of methyl phenyl sulfide (6a). However, the yield
for the oxidation product 6h was only 53%, although there was an
electron-donating amino group on the ortho-position of the phenyl ring.
Electron-withdrawing group on the phenyl ring (regardless of substitu-
tion position) (6d-6g) led to less efficient oxidation, the yields being at
medium level of 54–62%. Para-bromo phenyl methyl sulfide could be
oxidized at 62% yield (6e) and meta-bromo phenyl methyl sulfide was
oxidized with 58% yield (6f), while oxidation of ortho-bromo phenyl
methyl sulfide afforded only 54% product yield (6g). Oxidation of the
ethyl phenyl sulfide (2i) gives similar yield as that for methyl phenyl
sulfide (6a). The best oxidation yield was obtained with benzyl phenyl
sulfide, which was the highest of 89% (6j).
–
plane is 24.6(2)/15.0(3), indicating more bending of the ligand
compared to that in 1.
Quinones have been used as catalysts in oxidation reactions, and
therefore these lanthanide complexes were subjected to the investiga-
tion of catalytic studies for oxidation of thioethers. With methyl phenyl
sulfide as the reaction substrate, the optimized reaction conditions were
studied systematically over a variety of factors including catalysts, sol-
vents and oxidants (Table S3). Control experiment without catalyst
showed that hydrogen peroxide itself can oxidize thioether at limited
yield (Entry 1). K2AQDS catalyzes the oxidation in moderate yield while
no reaction occurs without oxidant (Entry 2 and 3). Only trace amount
of product was observed with O2 as the oxidant (Entry 4). Methanol is
the only one among the commonly used solvents which produces
satisfactory yield (Entries 5–10). Similar yields were obtained with 5%
or 10% catalyst (Entry 5 and 11). The optimal reaction conditions thus
obtained was the use of methanol as solvent and hydrogen peroxide as
oxidant with 5% catalyst. Screening of the catalyst with the optimal
reaction condition indicated that complex 4 has the best catalytic effi-
ciency (Table S4).
A possible reaction mechanism has been proposed for this oxidation
reaction (see Fig. 2) [43,44]. Our previous research over anthraquinone
derivative ligands indicated that their coordination complexes are good
catalysts for photooxidation reactions, based on the transformation
among the cycle of catalyst (M-L), photoexcited form (M-L*), and semi-
•
The catalysts have some solubility in methanol, although not good
enough to be fully soluble in the amount of solvent used for the reaction,
under which conditions the recovery rate of the catalyst was about 60%.
Therefore no cycle experiments were performed. The catalytic process
was believed to be homogenous, which means the amount of catalyst
that dissolved into the solvent actually catalyzed the reaction. This ex-
plains why the use of 5% and 10% molar ratio catalyst would lead to
almost the same yield (entry 5 and 11 in Table S3), because what takes
effect was those dissolved into the reaction medium (the amount of
solvent were the same for both reactions).
hydroquinone radical form (M-L(H) ) [38]. However in this case, the
complexes can catalyze the oxidation reaction without photoexicitation,
which can be correlated with the unique structure feature of the com-
plexes. As mentioned in the structural description, the ligands in all
these complexes take chelation mode, which results in remarkable steric
effect. One of the carbonyl groups bends out of the conjugated plane
significantly, dictating the fact that the generation of semi-
hydroquinone form would be much easier as compared to previous
cases without obvious structural bending. And this explains why this
series of complexes are able to catalyze the oxidation reaction without
any need of photooxidation.
Under the optimal reaction conditions, various thioether substrates
were investigated to study the versatility and substrate scope of this
4. Conclusions
Table 2
In summary, four lanthanide-potassium bimetallic coordination
complexes have been synthesized with anthraquinone-1,8-disulfonate as
the dianionic ligand. Single-crystal X-ray structure analysis revealed that
the complexes belong to two isostructural series, with rich hydrogen
Scope of thioethers.
bonding and π-π stacking interaction to stabilize the crystal packing. The
ligands in 1 and 2 chelate with either lanthanide or K+ ions while that in
3 and 4 chelate only with K+ ions, in addition to their bridging roles in
all cases. The chelation modes involving the coordination of carbonyl
group exerted significant steric effect to push the carbonyl group out of
the conjugation plane, resulting in easier hydrogenation to form the
semi-hydroquinone intermediate, which endows the complexes with
good catalytic properties toward oxidation of thioethers. Complex 4
among the series demonstrated the best catalytic efficiency over a wide
range of substrates.
Fig. 2. Proposed reaction mechanism of the oxidation reaction.
4

F.-Y. Cao et al.
Inorganic Chemistry Communications 130 (2021) 108682
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CRediT authorship contribution statement
Fu-Yu Cao: Investigation, Formal analysis, Methodology, Writing -
original draft. Meng-Ping Huang: Investigation. Hui-Lei Gao: Investi-
gation. Xiao-Li Zhao: Writing - review & editing. Jie Han: Writing -
review & editing. Xu-Dong Chen: Conceptualization, Supervision,
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Acknowledgments
This work was supported by the National Natural Science Foundation
of China (21671104, 22071110), the Priority Academic Program
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X-ray crystallographic data for complexes 1-4 have been deposited
with the Cambridge Crystallographic Data Center (CCDC Numbers
2059803 for complex 1; 2070118-2070120 for complex 2-4).
Supplementary data to this article can be found online at https://doi.
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