Three novel bismuth-based coordination polymers: Synthesis, structure and luminescent properties

Article abstract of DOI:10.1016/j.inoche.2017.06.018

Three novel bismuth-based coordination polymers, [(CH₃)₂NH₂][Bi(pdc)(bdc)]·2DMF, [(CH₃)₂NH₂][Bi(tdc)₂]·1.5DMF and [Bi(bpdc)₂H₂O]·xGuest (compounds 1–3) (H₂pdc = 3,5-pyridinedicarboxylic acid, H₂bdc = 1,4-benzenedicarboxylic acid, H₂tdc = 2,5-thiophenedicarboxylic acid, H₂bpdc = 4,4′-biphenyldicarboxylic acid), have been successfully synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction. Compounds 1 and 2, which are constructed by 9-coordinated or 8-coordinated Bi^{3 +}, feature three-dimensional structures with hms and dia topology, respectively. However, 5-coordinated Bi^{3 +} based compound 3 is a two-dimensional layered structure. Compound 1 can tune emissive performance by doping different lanthanide ions Tb^{3 +}, Eu^{3 +} and Dy^{3 +}. Furthermore, detection of nitro explosives is investigated. All of the compounds are characterized by elemental analysis, IR spectrum and thermogravimetric analysis.

Full text of DOI:10.1016/j.inoche.2017.06.018

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Inorganic Chemistry Communications xxx (2017) xxx–xxx
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Inorganic Chemistry Communications
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Short communication
Three novel bismuth-based coordination polymers: Synthesis, structure and
luminescent properties
Liang Kan, Jiantang Li, Xiaolong Luo, Guanghua Li, Yunling Liu ⁎
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Three
(CH
pyridinedicarboxylic acid, H
bpdc = 4,4′-biphenyldicarboxylic acid), have been successfully synthesized under solvothermal conditions
and characterized by single crystal X-ray diffraction. Compounds 1 and 2, which are constructed by 9-coordinat-
novel
bismuth-based
]·1.5DMF and [Bi(bpdc)
bdc = 1,4-benzenedicarboxylic acid, H
coordination
O]·xGuest (compounds 1–3) (H
tdc = 2,5-thiophenedicarboxylic acid,
polymers,
3 2 2
[(CH ) NH ][Bi(pdc)(bdc)]·2DMF,
Received 16 May 2017
Received in revised form 8 June 2017
Accepted 10 June 2017
Available online xxxx
[
3
)
2
NH ][Bi(tdc)
2
2
2
H
2
2
pdc
=
3,5-
2
2
H
2
3
+
ed or 8-coordinated Bi , feature three-dimensional structures with hms and dia topology, respectively. Howev-
Keywords:
Coordination polymer
Bismuth
Luminescence
Fluorescence quenching
Nitro explosives
er, 5-coordinated Bi3+ based compound 3 is a two-dimensional layered structure. Compound 1 can tune emissive
3
+
3+
3+
performance by doping different lanthanide ions Tb , Eu and Dy . Furthermore, detection of nitro explo-
sives is investigated. All of the compounds are characterized by elemental analysis, IR spectrum and thermogra-
vimetric analysis.
©
2017 Published by Elsevier B.V.
Porous coordination polymers (PCPs) or metal-organic frameworks
lanthanide ions into the structures due to similar radius, charges
and coordination numbers [7]. In addition, porous Bi-containing
MOFs with fluorescent properties can be used for fluorescence-
based detection.
In light of the above, in order to study the effect of coordination con-
figuration of bismuth on the structure and their luminescent properties,
we choose four simple organic ligands with higher symmetry, 3,5-
(
MOFs), which consist of metal ions and organic ligands, have received
much attention during recent years due to their various architectures
1], tunable pore size [2] and attractive properties [3]. However, most
of the works are mainly focused on transition metals which are usually
-coordinated or 6-coordinated or lanthanides due to their unique
[
4
properties in fluorescence and catalysis, while MOFs constructed by
main group metals, such as Bi3 , which possess a lone pair of electrons,
are rarely reported [4].
+
pyridinedicarboxylic acid (H
(H bdc), 2,5-thiophenedicarboxylic acid (H
biphenyldicarboxylic acid (H bpdc), to construct novel bismuth-based
2
pdc), 1,4-benzenedicarboxylic acid
2
2
tdc) and 4,4′-
Due to its geometrically flexible coordination environments, the
Bi3+ ion can be regarded as a novel node in the construction of
MOFs. From the viewpoint of coordination angle, the presence of
the lone pair of electrons affects the coordination angle of bismuth,
so that the polyhedral of Bi3 ion is generally distorted, which is
different from common octahedron and tetrahedron and so on [5].
From the perspective of coordination number, Bi3 ion commonly
has a variety of coordination numbers (as shown in Table S1),
which leads to unpredictability and diversity of bismuth-based
structures. For example, Norbert Stock and co-workers reported an
2
coordination polymers. Herein, three novel bismuth coordination poly-
mers have been synthesized and structurally characterized [8]. We fur-
ther explore the luminescent properties of compound 1 as lanthanide
host and effective detection of nitro explosive.
+
Compound 1 is synthesized by Bi(NO
under solvothermal conditions at 105 °C [9]. Single crystal X-ray
diffraction analysis reveals that compound crystallizes in
hexagonal system with P-62m space group and features a three-di-
mensional (3D) structure composed of H pdc and H bdc mixed
3 2 2 2 2
) ·5H O, H pdc and H bdc
+
1
2
2
8
-coordinated bismuth-based MOF constructed from simple
ligands. Powder X-ray diffraction (PXRD) pattern of compound 1
confirms high purity of the synthesized samples (Fig. S1a). As
building units, it reveals unprecedented topological complexity
with only one unique node [6].
Moreover, bismuth-based MOFs always exhibit noticeable optical
and catalytic properties. Some of them can be treated as lanthanide
hosts to tune the emissive performance by doping different
3
+
shown in Fig. 1a, each Bi ion is nine-coordinated with one nitrogen
atom from pdc2 anion and eight oxygen atoms from four carboxylic
acid groups, to form a distorted hexahedron geometry. The Bi\\O
and Bi\\N distances are in the range of 2.354–2.740 Å, which are
similar to the reported results. Fig. 1a clearly shows the process of
construction of 3D structure by using mixed ligand strategy. Each
−
⁎
Corresponding author.
pdc2 anion connects three Bi
−
3+
ions through two carboxylic acid
E-mail address: yunling@jlu.edu.cn (Y. Liu).
http://dx.doi.org/10.1016/j.inoche.2017.06.018
387-7003/© 2017 Published by Elsevier B.V.
1
Please cite this article as: L. Kan, et al., Three novel bismuth-based coordination polymers: Synthesis, structure and luminescent properties, Inorg.
Chem. Commun. (2017), http://dx.doi.org/10.1016/j.inoche.2017.06.018

2
L. Kan et al. / Inorganic Chemistry Communications xxx (2017) xxx–xxx
Fig. 1. Description of the structures of compound 1: (a) the formation of a 3D framework
by mixed ligands strategy; (b) the (3, 5) connected hms topology; (c) the 1D channels
along [001] direction. Color code: carbon: gray; nitrogen: blue; oxygen: red; bismuth:
green. (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)
Fig. 2. Description of the structures of compound 2: (a) Bi3+ ion viewed as a 4-connected
node with distorted tetrahedron, the ligand H tdc viewed as a 2-connected node; (b) the
D framework of compound 2; (c) the 2-fold interpenetrated 4-connected dia topology;
d) the 1D channels along [010] direction; (e) the 1D channels along [001] direction.
2
3
(
groups and one nitrogen atom, generating a two-dimensional (2D)
honeycomb layer. The 2D layer is further connected by bdc2 ligand
Color code: carbon: gray; nitrogen: blue; oxygen: red; sulfur: yellow; bismuth: green.
(For interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.)
−
3
+
to form a 3D framework. From a topological point of view, the Bi can
2
−
be regarded as a 5-connected node, pdc ligand can be regarded as a 3-
2
−
connected node and bdc
ligand can be regarded as a 2-connected
stacking of the 2D layers, compound 3 possesses one type of channel
with diameters of 11 × 11 Å excluding the van der Waals radius.
The thermal stabilities of compounds 1–3 are investigated by
thermogravimetric analysis (TGA) (Fig. S2). For compound 1, the first
step weight loss of 26.4% below 335 °C belongs to the removal of
dimethylamine cation and DMF molecule (calcd: 26.3%). Upon further
heating, the weight loss between 335 and 480 °C belongs to the
node, compound 1 adopts (3, 5) connected hms topology (Fig. 1b).
Compound 1 possesses two types of channels with diameters of 2.5 and
4
.5 Å excluding the van der Waals radius, respectively (Fig. 1c).
Compound 2 is synthesized by the solvothermal reaction of
Bi(NO ·5H O with H tdc in the mixture of dimethylformamide
DMF) and methanol [10]. Single crystal X-ray diffraction analysis
3
)
3
2
2
(
reveals that it crystallizes in monoclinic system with C2/c space
group. The purity of compound 2 is confirmed by PXRD patterns
3
+
(
Fig. S1b). The Bi
ion is eight-coordinated with eight oxygen
2
−
atoms from four tdc
ligands respectively. The Bi\\O distances
are in the range of 2.243–2.700 Å, these bond parameters are close
to those in other reported complexes. To better understand the
3
+
structure of compound 2, the Bi ion can be regarded as a 4-connected
2
−
node, tdc
ligand can be regarded as a 2-connected node (Fig. 2a),
therefore, the framework of compound 2 can be described as a 2-fold
interpenetrated dia topology (Fig. 2c). There are two kinds of channels
in the structure of compound 2, the size of the channels are about 5 × 6
and 6 × 6 Å excluding the van der Waals radius, respectively (Fig. 2d
and e).
3 2 2 2
Compound 3 is synthesized by Bi(NO ) ·5H O and H bpdc under
solvothermal conditions at 85 °C [11]. Single crystal X-ray diffraction
analysis reveals that compound 3 crystallizes in tetragonal system,
space group P4/nmm with a 2D framework. The agreement between
the as-synthesized and simulated PXRD patterns indicates the phase
purity of the product (Fig. S1c). Different from compounds 1 and 2,
each Bi3 ion in compound 3 connects four bpdc
+
2−
anions through
Fig. 3. Description of the structures of compound 3: (a) Bi3+ ion viewed as a 4-connected
quadrilateral node, the ligand H bpdc viewed as a 2-connected node; (b) schematic
2
representation of the topology and the 2D layer along [001] direction. Color code:
carbon: gray; nitrogen: blue; oxygen: red; bismuth: green. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this
article.)
carboxylic acid groups and one solvent molecule in the axial
direction (Fig. 3a). With the additional influence of lone pair of
electrons, the spatial configuration of the four B i\ \O bonds tends to
3
+
be flat, so Bi
can be regarded as a quadrilateral node, forming a
2
D structure eventually with a sql topology (Fig. 3b). With the -AA-
Please cite this article as: L. Kan, et al., Three novel bismuth-based coordination polymers: Synthesis, structure and luminescent properties, Inorg.
Chem. Commun. (2017), http://dx.doi.org/10.1016/j.inoche.2017.06.018

L. Kan et al. / Inorganic Chemistry Communications xxx (2017) xxx–xxx
3
Fig. 4. (a) Emission spectra of compound 1 excited at 313 nm in solid state at room temperature; (b) Tb, Eu, Dy doped compound 1 excited at 330 nm in solid state at room temperature.
decomposition of ligands. The final residue of 31.6% is attributed to
Bi powder (calcd: 28.6%). For compound 2, the initial weight loss
(2,4-DNP) and 4-nitrophenol (4-NP) (Fig. 5). The fluorescent
quenching efficiency was analysed by using the Stern-Volmer (SV)
2 3
O
below 230 °C belongs to the removal of guest molecules. Upon further
heating, the weight loss between 230 and 540 °C belongs to the decom-
position of ligands. The final residue of compound 2 at 800 °C is attrib-
equation (I
0
/ I) = 1 + Ksv[Q], where Ksv is the quenching constant
−
1
(M ), [Q] is the molar concentration of the explosives, I and I are
the luminescence intensities of compound 1 before and after the ad-
0
uted to Bi O
2 3
powder. For compound 3, the weight loss below 600 °C
dition of the explosives, respectively. As shown in Fig. S6, the SV
can be attributed to the loss of guest molecules, coordinated water mol-
ecules and organic ligands. The final residue at 800 °C is attributed to
plots are almost linear at low concentration range. Compound 1
has the high Ksv values of 4.91 × 104
M
−1
toward TNP, 4.57
× 104
M
−1
toward 2,4-DNP and 3.70 × 10 M−1 toward 4-NP, re-
4
Bi O
2 3
powder.
The luminescent properties of compound 1 were investigated.
The solid-state emission spectra of compound 1 reveals that it
spectively. The different quenching efficiencies can be attributed to
electron and energy transfer and electrostatic interactions in the
host-guest systems [13].
emits blue light when excited at 313 nm (Fig. 4a). The doped
samples are synthesized by doping Tb3 , Eu
+
3+
and Dy
3+
during
In summary, three novel coordination polymers based on
bismuth have been successfully synthesized under solvothermal
conditions. The high coordination number metal bismuth-based
compounds 1 and 2 feature 3D structures, but compound 3 based
on 5-coordinated bismuth is a 2D layer structure. It was found that
the lone pair of electrons and various coordination numbers of
bismuth have significant effects on the construction of complex
bismuth-based MOFs. In addition, compound 1 can be used for
detection of TNP, 2,4-DNP and 4-NP, and doping lanthanide ions
into bismuth-based compounds is also an effective way to obtain
functional luminescent materials.
the synthesis process [12]. As shown in Fig. S4, PXRD patterns
indicates that the structure of compound 1 don't change after
doping lanthanide ions. Tb3 , Eu
+
3+
and Dy
emit intense green, red and blue luminescence when excited at
30 nm, respectively (Fig. 4b), which reveals that doping
3+
doped compound 1
3
lanthanide ions into bismuth-based MOFs is an effective way to
tune the luminescent performance.
Taking into account the strong luminescent properties of
compound 1 and the electron transfer between π-electron-rich
fluorescent compounds and electron-deficient analyte in the
fluorescence quenching processes, we further investigate the
detection of nitro explosives. Emission spectra of compound 1
dispersed in DMF exhibits intense emission at 414 nm when excited
at 313 nm (Fig. S5). However, the fluorescent quenching is observed
by the addition of 2,4,6-trinitrophenol (TNP), 2,4-dinitrophenol
Acknowledgment
The authors gratefully acknowledge the financial support of the
National Natural Science Foundation of China (No. 21373095).
Fig. 5. Effect on the emission spectra of compound 1 dispersed in DMF upon incremental addition of a selected explosive (1 mM, 20 μL addition each time; inset: SV plots of selected
explosive).
Please cite this article as: L. Kan, et al., Three novel bismuth-based coordination polymers: Synthesis, structure and luminescent properties, Inorg.
Chem. Commun. (2017), http://dx.doi.org/10.1016/j.inoche.2017.06.018

4
L. Kan et al. / Inorganic Chemistry Communications xxx (2017) xxx–xxx
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Appendix B. Supplementary material
synthesis and characterisation of two new bismuth metal organic frameworks,
CrystEngComm 16 (2014) 5560–5565;
CCDC 1545100–1545102 containing the supplementary crystallo-
graphic data for this paper can be obtained free of charge from the Cam-
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tion range can be found online at doi: http://dx.doi.org/10.1016/j.
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