Lead(II) arenedisulfonate coordination polymer: Synthesis, crystal structure and properties

Article abstract of DOI:10.1016/j.inoche.2013.06.006

A new 1-D coordination polymer, {[Pb(Phen)(1,5-nds)(H₂O) ₂]·H₂O}_n (1), was constructed from 1,5-naphthalenedisulfonate (1,5-nds), 1,10-phenanthroline (Phen) and Pb(CH ₃COO)₂·3H₂O

Full text of DOI:10.1016/j.inoche.2013.06.006

Inorganic Chemistry Communications 35 (2013) 192–194
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Lead(II) arenedisulfonate coordination polymer: Synthesis, crystal
structure and properties
b
c
a,b,
a
c
Li Wang a, , GuanFeng Li , Mengjie Liu , Dongsheng Deng
⁎
⁎
, Yamei Pei , Xinyi Wang
a
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education and School of Chemistry, Central China Normal University, Wuhan 430079, PR China
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, PR China
Institute of Resources & Environment, Henan Polytechnic University, Jiaozuo 454150, PR China
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
A new 1-D coordination polymer, {[Pb(Phen)(1,5-nds)(H2O)2]·H2O}n (1), was constructed from 1,5-
naphthalenedisulfonate (1,5-nds), 1,10-phenanthroline (Phen) and Pb(CH3COO)2·3H2O with easily reach-
able lead sites, which can be subsequently used to promote the epoxide ring-opening reaction of epoxides
and amines with remarkable catalytic activity. In addition, the thermal and luminescent properties of 1 in
the solid state were also investigated.
Received 26 March 2013
Accepted 6 June 2013
Available online 22 June 2013
Keywords:
© 2013 Elsevier B.V. All rights reserved.
Coordination polymers
Organosulfonate
Crystal structure
Epoxide ring-opening
In recent years, coordination polymers (CPs) have gained much
attention due to their potential applications as heterogeneous cata-
lysts, magnetic and luminescent materials, and so on [1–4]. In gener-
al, CPs can behave as catalysts through (a) the metallic component
containing the coordinatively unsaturated sites [5,6], or (b) ligands
functionalized with organic groups [7,8]. In the former case, CPs can
act as Lewis-acid catalysts because of the Lewis acidity of metal cat-
ions (Mn+) [9,10]. As is well known, polycarboxylate compounds
have been the most frequent choice of ligands for the design and con-
struction of functional CPs due to their versatile coordination modes
[11,12]. In contrast to the flourishing studies of organocarboxylate,
the coordination chemistry of organosulfonate is relatively rare, prob-
ably for their weak coordinating ability, although they have similar
structures [13]. However, organosulfonates are important ligands,
which can also provide a nice opportunity for the construction of un-
usual CPs [14–18].
On the other hand, epoxide ring-opening reactions, which provide
important synthetic tools for generating stereo-controlled fine
chemicals, have been the focus of significant recent interest [19]. Ac-
cording to recent MOF reviews [3,20], two Cu-CPs were successful as
heterogeneous catalysts for amino alcohol synthesis. The MOFs were
found to be size selective, but they displayed modest conversions
(b50%) and no evidence was provided about robustness of these cat-
alysts. One of our goals is to design and synthesize functionalized CPs,
which can provide coordinatively unsaturated sites for the activation
of incoming organic substrate. Herein, we report the synthesis and
structure of one new Pb(II) arenedisulfonate coordination polymer,
{[Pb(Phen)(1,5-nds)(H2O)2]·H2O}n (1). Furthermore, the catalysis
toward epoxide ring-opening reaction, and the luminescent and ther-
mal properties has been determined as well.
Using hydrothermal methods, the crystalline compounds
(1) were successfully obtained by the reaction of disodium
1,5-naphthalenedisulfonate (1,5-nds) and 1,10-phenanthroline (Phen)
with Pb(CH3COO)2·3H2O, and characterized as having the formula
{[Pb(Phen)(1,5-nds)(H2O)2]·H2O}n, basing on elemental analysis result
and further confirmed by the single-crystal X-ray diffraction analysis.
The structural analysis indicates that CP 1 crystallized in the Pī space
group of the triclinic system and the asymmetric unit of CP 1 contains
one Pb(II), two terminal waters, one free water, one phen group, and
one 1,5-nds anion. The unique Pb(II) ion is six-coordinated by one
1,5-nds group, two waters, and one chelating phen groups in a distorted
five pyramid geometry (Fig. 1(a)). Around each Pb atom, there exist four
strong Pb\O bonds (ranging from 2.546(7) to 2.659(7) Å) and two
strong Pb\N bonds (2.451(7) and 2.526(7) Å) (Table S2). The four
oxygen atoms and two nitrogen atoms are located on one side of the
Pb(II) ion, which adopts
a hemidirected structural arrangement,
suggesting the presence of a stereochemically active lone electron pair
around the metal ion. The neighboring Pb centers are linked together
by two O atoms of 1,5-nds anion to generate an infinite 1-D chain
with a Pb⋯Pb separation of 7.297 Å (Fig. S1). Further, these 1-D chains
are connected by H-bonds from free water to sulfonate and terminal
water to sulfonate, giving rise to a 2-D sheet (Fig. 1(b)) along
the ac plane. The H-bond details for 1 are given in Table S3. These
hydrogen positions and H-bonds meet the requirement described in
the literature [21].
⁎
Corresponding authors. Tel./fax: +86 379 65523821.
E-mail addresses: wl_928@mail.ccnu.edu.cn (L. Wang),
dengdongsheng168@sina.com (D. Deng).
1387-7003/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.inoche.2013.06.006

L. Wang et al. / Inorganic Chemistry Communications 35 (2013) 192–194
193
Fig. 1. (a) The asymmetric unit of 1 along with the atom numbering scheme (symmetry code: (A) x − 1, y, z). (b) View of 2-D sheet in 1.
The thermogravimetric analysis (TGA) revealed that 1 was stable
up to 410 °C (Fig. S2). The TG curve of 1 exhibits three weight loss
stages. The first of 7.8% at 25–115 °C corresponds to release of two co-
ordinated water molecules and one lattice water (calcd 7.4%). The
second and third weight losses at 414–860 °C can be attributed to
the decomposition of the framework, forming PbO as a final product
(observed 30.2%, calcd 30.7%). The pure polymer 1 was confirmed
by powder X-ray diffraction (PXRD) measurement in which diffrac-
tion peaks of experimental data are in excellent agreement with the
simulated data from single-crystal X-ray data (Fig. S3). After a sample
of 1 was treated under vacuum at 140 °C for 4 h, a PXRD analysis of
the resultant crystalline solid 1′ showed a sharp diffraction pattern
that is similar to that of the as-synthesized sample (Fig. S4). This re-
sult indicates that the framework was maintained after removal of
the water molecules.
Emission behavior of polymer 1, 1,5-nds and Phen was studied in
solid state at room temperature (Fig. 2). Phen and 1,5-nds employed
to synthesize polymer 1 exhibit good fluorescent emission at 441 nm
(λex = 380 nm) and 394 nm (λex = 345 nm), respectively. Upon
excitation at 402 nm, 1 displayed an emission band at 456 nm,
which showed a red shift relative to 441 nm (λex = 380 nm) of
phen and to 394 nm (λex = 345 nm) of 1,5-nds. The origin of this
emission may be assigned as the metal-to-ligand charge transfer
(MLCT) with electrons being transferred from Pb2+ lone pair to the
unoccupied π* orbitals of the two ligands [22–24].
to catalyze organic reactions, similar to that in literatures [25,26].
Thus, the CP 1 was examined for the possible Lewis-acid-type catalyt-
ic performance as heterogeneous catalysts for aminolysis reaction of
epoxides. The results are summarized in Table 1. It is noted that the
CP 1 showed good catalytic properties (Table 1, entries 1–9). The prod-
uct yields are little sensitive to reaction substrates in the experiment.
Several control experiments were performed to confirm that the
CP 1 was indeed the catalytic source for epoxide ring-opening. In ini-
tial control reactions without CP 1, the reaction did not proceed at all,
whereas the use of Pb(CH3COO)2·3H2O resulted in litter conversion.
Likewise, when the catalyst was filtered off, the reaction was no lon-
ger promoted. These control experiments strongly suggest that the
soluble and catalytically active species are not leached out from the
networks. Thus, the reaction was promoted by heterogeneous cataly-
sis of CP 1. Furthermore, several tests were also performed with CP 1
to understand their chemical stability post-catalysis. Overall, CP 1 can
be recovered by simple filtration and reused several times (tested
three consecutive times) without much loss of activity (~3% drop in
the third run). Thus, the recovered CP remained stable with complete
retention of reactivity, which is further confirmed by PXRD analysis.
As shown in Fig. S4, the recovered material shows no change in the
structure of the catalyst.
In summary, a new arenedisulfonate coordination polymer 1 with
easily reachable lead sites has been obtained. Further research dem-
onstrates that the Lewis acidic Pb2+ ions in the resultant networks
display high catalytic activity in the epoxide ring-opening reaction
of epoxides and amines.
The crystal structure analysis reveals the presence of a stereo-
chemically active lone electron pair around the metal ion in CP 1.
The feature implies that CP 1 could be used as catalytically active CP
Acknowledgment
We gratefully acknowledge the financial support from the National
Natural Science Foundation of China (Grant No. 21272109), the Natural
Table 1
The ring-opening reactions of epoxides with amines catalyzed by 1.a
Entry
Epoxide
Amine yieldb (%)
1
2
3
4
5
6
7
8
9
Styrene oxide
Styrene oxide
Styrene oxide
Cyclohexene oxide
Cyclohexene oxide
Cyclohexene oxide
Cyclopentene oxide
Cyclopentene oxide
Cyclopentene oxide
Aniline
94
93
93
92
90
90
91
90
90
2-Chloroaniline
2-Methylaniline
Aniline
2-Chloroaniline
2-Methylaniline
Aniline
2-Chloroaniline
2-Methylaniline
a
Conditions: a mixture of epoxide (0.5 mmol), aniline (0.5 mmol) and 1 (0.01 mmol)
under solvent-free was stirred at temperature for 2 h.
b
Fig. 2. Emission spectra of polymer 1 and its constituting ligands.
Isolated yield.

194
L. Wang et al. / Inorganic Chemistry Communications 35 (2013) 192–194
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Appendix A. Supplementary material
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The details of X-ray diffraction, analytical and spectral data collec-
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