Two PbII-based coordination polymers based on 5-aminonicotinic acid and 5-hydroxynicotinic acid for Knoevenagel condensation reaction and luminescent sensor

Article abstract of DOI:10.1016/j.jssc.2019.120927

Two new Pb^II-based coordination polymers based on 5-aminonicotinic acid (namely HL–NH₂) and 5-hydroxynicotinic acid (namely HL–OH) are both successfully synthesized under solvothermal synthesis conditions. PbCl₂ and HL-NH<

Full text of DOI:10.1016/j.jssc.2019.120927

Journal of Solid State Chemistry 278 (2019) 120927
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Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
Two PbII-based coordination polymers based on 5-aminonicotinic acid and
5-hydroxynicotinic acid for Knoevenagel condensation reaction and
luminescent sensor
,
,
,
,c
Xiuling Zhang a *, Ranhui Zhang a b, Yaoqiang Jin a b, Tingting Li a
a College of Chemistry and Chemical Engineering, Dezhou University, Dezhou, 253023, PR China
b College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao, 266000, PR China
c College of Chemical Engineering, Xi’an Polytechnic University, Xi’an, 710048, PR China
A R T I C L E I N F O
A B S T R A C T
Two new PbII-based coordination polymers based on 5-aminonicotinic acid (namely HL–NH2) and 5-hydroxyni-
cotinic acid (namely HL–OH) are both successfully synthesized under solvothermal synthesis conditions. PbCl2
and HL-NH2 can generate a 3D network with the formula of {[Pb3(L-NH2)2Cl5]⋅(H2O)}n (complex 1). The –NH2
functional group is replaced by –OH on the organic linker to further coordinate with PbII to fabricate another 3D
framework of [Pb2(L–O)Cl2]n (complex 2). Interestingly, various and fanatics structures can be tuned and regu-
lated by different functional substituent groups. Furthermore, complex 1 can be applied as a high-efficient het-
erogeneous catalysis for Knoevenagel condensation reaction. Meanwhile, complex 2 is an excellent potential
Keywords:
PbII-Based coordination compound
Luminescent sensor
Catalysis
Fe3þ
luminescent sensor for Fe3þ
.
1. Introduction
applied as a good candidate to catalyse Knoevenagel condensation re-
action [41–44]. Meanwhile, MOFs based on 5-hydroxynicotinic acid can
be used as luminescent sensors to detect hazardous substances. Herein, a
systematic study is investigated and reported to design and synthesize
two three-dimensional (3D) PbII MOFs, including complex 1 based on
5-aminonicotinic acid (namely HL–NH2) and complex 2 based on
5-hydroxynicotinic acid (namely HL–OH). More importantly, complex 1
can be used a heterogeneous catalyst for Knoevenagel condensation re-
action, meanwhile complex 2 can be considered as a luminescent sensor
for Fe3þ with good recyclability.
In these decades, a good deal of efforts have been directly focused on
tuning and designing coordination compounds, also called metal–organic
frameworks (MOFs) [1–4], which is not only due to their various net-
works and widely potential applications in lots of fields, including
catalysis [5–8], optical device [9–11], fluorescent sensor [12–15],
enzyme carriation [16–18], and gas adsorption or separation [19–23].
Nevertheless, it is a significant challenge to really understand structures
and properties relationships at the present investigate stage. In the view
of crystal engineering, organic linkers with different coordinated sites
and structures are considered as the most important factor to construct
coordination compounds [24–28]. On the other hand, chemical and
physical factors all can affect the final structures, such as solvent, pres-
sure, template, temperature, pH value and so on [29–35]. –NH2 and –OH
functional groups are always introduced in linkers to affect the structures
and properties, because they have different coordination abilities and
acid-base property. Different structures and functional groups can
directly affect their physicochemical performances. The displacement
result of hydrogen atom by –NH2 and –OH functional groups will have
remarkable influences in many aspects, especially catalytic and gas
sorption [36–40]. In the other previous reports, –NH2 group can be
2. Experimental
2.1. Materials and general methods
All chemicals and reagents were purchased from reagent companies
and used directly in this work. All powder X-ray diffraction (PXRD) were
achieved from a Riguku D8 ADVANCE with Cu-K
α
(λ ¼ 1.5418 Å) from 5ꢀ
to 50ꢀ of 2θ value. Elemental analyses (C, H, and N) were analysed on a
VarioEL cube analyzer. Thermogravimetric analyses (TGA) data weꢁre1
acquired on a TGA Q500 machine in a N2 condition with 10 ꢀC min
heating rate. The catalytic data were calculated by GC method on a
* Corresponding author.
E-mail address: xlzhang99@126.com (X. Zhang).
https://doi.org/10.1016/j.jssc.2019.120927
Received 28 July 2019; Received in revised form 18 August 2019; Accepted 22 August 2019
Available online 26 August 2019
0022-4596/© 2019 Elsevier Inc. All rights reserved.

X. Zhang et al.
Journal of Solid State Chemistry 278 (2019) 120927
TRACE 1300 instrument. Luminescent spectra were obtained on a Cary
Eclipse fluorescence spectrophotometer. UV–Vis absorption spectra were
performed on a UV-1200UV-1100.
Table 1
Crystal data and structure refinement for 1 and 2.
Compound
1
2
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C12H6O5N4Cl5Pb3
1085.12
monoclinic
P21/n
13.9215 (16)
8.2851 (9)
19.683 (2)
90
107.424 (2)
90
2166.1 (4)
4
C6H3O3NCl2Pb2
622.37
2.2. Syntheses of complex 1 and 2
orthorhombic
P212121
8.0846 (17)
8.8824 (18)
13.903 (3)
90
90
90
998.4 (4)
4
4.140
2.2.1. Preparation of {[Pb3(L-NH2)2Cl5]⋅(H2O)}n (complex 1)
PbCl2 (20 mg) and HL-NH2 (8 mg) were both dissolved in a mixture
solution of CH3CN (2.5 mL) and H2O (1.5 mL), which was heated at
100 ꢀC for 5 days in a Telfon-lined stainless steel vessel under an
autogenous pressure. After the reaction vessel was gradually cooled
down to room temperature, light yellow single crystals with well shape of
complex 1 were collected and dried in air with a 59% yield based on HL-
NH2. Anal. Calcd for C12H8O5N4Cl5Pb3: C, 13.3; H, 0.7; N, 5.2%. Found:
C, 13.4; H, 0.6; N, 5.2%.
b (Å)
c (Å)
α
(º)
β (º)
γ (º)
V (Å3)
Z
ρ
μ
(calc g cmꢁ3
)
3.327
23.915
3820
(mmꢁ1
)
34.192
1759
Nref
R (int)
0.0666
0.0500
Goodness-of-fit on F [2]
R1, wR2 [I > 2 (I)]
R1, wR2 (all data)
1.029
0.0343, 0.0630
0.0487, 0.0681
0.981
0.0239, 0.0543
0.0247, 0.0547
2.2.2. Syntheses of [Pb2(L–O)Cl2]n (complex 2)
σ
A mixture of HL–OH (8 mg), PbCl2 (25 mg) was putted in CH3CN
(2.5 mL) and H2O (1.5 mL), which was further added 0.1 mL of NaOH
(0.1 M). The resultant mixture was heated at 100 ꢀC for 4 days in a sealed
Telfon-lined stainless steel vessel. After it was slowly cooled down to
room temperature, yellow block crystals with good quality can be
Fig. 1. (a) Coordination environment of PbII; (b and c) coordination modes of L–NH–2 ligand; (d) viewing of the 2D layer; and (e–g) 3D structures in different axises (all
hydrogen atoms are omitted for clarity, and C, black; O, red; N, blue; Cl, purple; Pb, green). (For interpretation of the references to colour in this figure legend, the
reader is referred to the Web version of this article.)
2

X. Zhang et al.
Journal of Solid State Chemistry 278 (2019) 120927
Fig. 2. (a) Coordination environment of PbII cation in complex 2; (b) coordination mode of L–O2– ligand; and (c–e) viewing of 3D structure along different axises (all
hydrogen atoms are removed for clarity, and C, black; O, red; N, blue; Cl, purple; Pb, green). (For interpretation of the references to colour in this figure legend, the
reader is referred to the Web version of this article.)
achieved in
a
63% yield based on HL-OH. Anal. Calcd for
experiments. All emission intensities of the above dispersions were per-
C6H3O3NCl2Pb2: C, 11.6; H, 0.5; N, 2.3%. Found: C, 11.3; H, 0.4; N, 2.2%.
formed and collected in different DMF solutions of M(NO3)x (Mxþ ¼ Liþ,
Naþ, Kþ, Agþ, Zn2þ, Mn2þ, Mg2þ, Cd2þ, Ca2þ, Co2þ, Cu2þ, Ni2þ, Fe2þ
,
and Fe3þ, 5.0 ꢂ 10ꢁ4 mol Lꢁ1) after immersing 2 min.
2.3. X-ray structure determination and structure refinement
Single crystal data of 1 and 2 were both measured on a Bruker SMART
CCD diffractometer with Mo Kα radiation (λ ¼ 0.71073 Å). Crystal
frameworks can be located precisely by the direct approach with SHELXT
6, which was further refined by using the full-matrix least-squares tech-
nique with SHELXL-2015 [45,46] and OLEX2 software [47]. In addition,
all non-hydrogen atoms were confirmed by using anisotropic displace-
ment parameters. Table 1 summarizes in all crystal data.
2.7. The typical luminescence titration for complex 2
Powder crystal 2 was carefully putted in 3 mL DMF to generate
1.0 mg mLꢁ1 suspension in a quartz cell, which was used for all sensing
titration trials. The titration experiments were measured by slowly
introducing Fe3þ and further repeated at least three times.
3. Results and discussion
2.4. Typical catalysis procedure
3.1. Structural description for complex 1
Complex 1 was dried in air and then soaked in toluene for 1 day prior
the catalytic reaction. In a typical procedure, substrate (1 mmol) and
malononitrile (1.1 mmol) were both mixed in a round-bottom flask with
toluene (5 mL). The reaction mixture was heated and kept at 85 ꢀC.
Complex 1 (~100 mg) was added into the above reaction system and
slowly stirred under this condition. The final catalytic yields can be
calculated by the GC method.
Single-crystal X-ray diffraction data obviously exhibit that complex 1
crystallizes in monoclinic crystal system and P21/n space group. As seen
in Fig. S1, the asymmetric unit has three PbII atoms, five Clꢁ atoms, two
crystallographically independent L–NH–2 ligands and a free O atom. As
shown in Fig. 1a, Pb1 atom is linked with seven atoms, including two O
atoms from a cheating carboxylate group, four Clꢁ atoms, and one N
atom from –NH2, respectively. Pb2 atom is connected with six atoms,
including an oxygen atom from a cheating carboxylate group, four Clꢁ
atoms, and one N atom from –NH2, respectively. Pb3 is surrounded by
five coordinated atoms from two Clꢁ atoms, two atoms from a cheating
carboxylate group, and one N atom from –NH2, respectively. The
2.5. Recyclable catalysis experiment
The recyclability of 1 can be easily regenerated by centrifugation and
washing by fresh toluene for several times. The re-collected samples were
further reused as a catalyst for the continuous catalytic reaction.
deprotonated L–NH–2 ligands adopt two different coordination modes μ3
-
η2 η1 η1 and μ2 η1 η1 1, which are on a scale of one to one in the
:
:
-
:
: η
2.6. Luminescent sensing experiments
structure (Fig. 1b and c). As illustrated in Fig. 1d, complex 1 has a two
dimensional (2D) layer by using bridging Clꢁ. Furthermore, there
different layers can be further connected by –COO– groups of bridging
linkers to construct a 3D network (Fig. 1e–g).
Single crystal data of as-synthesized complex 2 shows that it is the
orthorhombic crystal system with the P212121 space group. In its
As-synthesized 2 was ground several minutes in a mortar to signifi-
cantly reduce the size before all sensing trials. Ground 2 was selected and
studied for luminescent detectable experiments. Ground 2 (3.0 mg)
firstly well dispersed in 3.0 mL N, N-dimethylformamide (DMF) for next
3

X. Zhang et al.
Journal of Solid State Chemistry 278 (2019) 120927
Fig. 3. (a) PXRD profiles of simulated and as-synthesized samples; and (b) TGA curves of fresh as-synthesized samples.
Table 2
asymmetric unit, complex 2 owns two PbII atoms, two crystallographi-
cally independent Clꢁ atoms, and one full deprotonated L–O2ꢁ bridging
ligand (Fig. S2). As found in Fig. 2a, there are two significantly different
PbII centers in the whole structure. Pb1 is surrounded by six atoms from
four oxygen-donors from one –Oꢁ and two –COOꢁ groups, and two Clꢁ
atoms, while Pb2 is connected by five atoms from one –Oꢁ and two
–COOꢁ groups, one nitrogen-donor from pyridine, and one Clꢁ bridging
atom. Fig. 2b shows that only one coordination mode of the L–O2ꢁ
bridging ligand in complex 2, which is connected with six PbII atoms by
Results of Knoevenagel condensation reactions based on different aldehyde re-
actants.
Entry
1
Substrate
Product
Yield (%)
>99
the coordination mode as μ6- : : : η
η2 η1 η2 2. As shown in Fig. 2c–e, all PbII
centers are linked with each other by nitrogen and oxygen-donors from
the L–O2ꢁ bridging ligands to construct a new 3D network, which is
remarkably different network with that of complex 1 due to the different
organic functional groups.
2
3
8
>99
3.2. PXRD and thermal analysis
4
5
6
>99
81
PXRD profiles of fresh 1 and 2 were both measured in solid state at
room temperature. The characteristic peaks of achieved samples are
matched very well with the simulated PXRD patterns. The measurement
results evidently show that as-synthesized block samples are the phase
purities and same with the obtained single crystal (Fig. 3a). TGA curves
of as-synthesized 1 and 2 are both shown in Fig. 3b, clearly displaying
that they are able to keep their whole constructions at relative high
temperature. The first weight loss of complex 1 is probably ascribed to
removing guest and coordinated molecules. The second weight loss of
complex 1 and the weight reduction of complex 2 are mainly attributed
to structure collapse and disintegration at high temperature. The above
72
Fig. 4. The kinetic rate (a) and the recyclability (b) of complex 1 for this reaction.
4

X. Zhang et al.
Journal of Solid State Chemistry 278 (2019) 120927
Fig. 5. Luminescence spectra of free HL–OH linker (a) and complex 2 (b) in solid state; (c) emission spectra of complex 2 in different organic solvents; and (d)
emission intensities of ground 2 in DMF for one day.
results clearly prove that as-synthesized 1 and 2 both have relatively
good thermal stabilities.
aldehyde reactants with large size and electron-donor –OMe group can
remarkably decrease the catalytic yields to 81% and 72% for one –OMe
group (entry 5) and two –OMe groups (entry 6) as substituent groups,
respectively.
Reusability is also a vital element to appraise heterogeneous catalysts
for real applications. Catalyst 1 is easily re-collected by fast centrifuga-
tion at 10000 r⋅minꢁ1 about 2 min and further washing with fresh
toluene carefully for some times. As displayed in Fig. 4b, the catalytic
ability of reused complex 1 can preserve well due to its good stability.
PXRD data of reused 1 after four times obviously illustrated that the
framework of recycled sample can keep very well during the catalytic and
recycle process (Fig. S3).
3.3. Catalytic properties
By virtue of Lewis base catalytic centers in complex 1 from single
structure, the obtained 1 is able to investigate and consider as a catalyst
for the classical Knoevenagel condensation reaction as a chemical reac-
tion model (Table 1) [41–44]. Firstly, fresh 1 was carefully immersed in
toluene overnight and then dried in air before reaction. In a represen-
tative catalytic process, the substrate of this reaction with different
functional groups (1 mmol) and malononitrile (1.1 mmol) were both
added in a round-bottom flask with toluene (5 mL). After complex 1
(~100 mg) was added into the above reaction system and slowly stirred
at 85 ꢀC for 5 h in an oil bath. Table 2 has all catalytic results of various
substrates in this work. As illustrated in entry 1, the catalytic yield of
2-benzylidenemalononitrile product is almost 100% completely. Mean-
while, this reaction was selected and studied as an organic reaction
model to explore the kinetic rates (Fig. 4a). The results clearly exhibit
that this studied reaction is almost complete reaction after 5 h. To
confirm the necessity of catalyst 1 for this Knoevenagel condensation
reaction, the catalytic reaction is immediately terminated after dislodg-
ing catalysis 1. The terminal catalytic yield is only 8% without 1 (entry
2). It is distinctly ensured that complex 1 is prerequisite for this reaction
and plays a significant role to trigger this reaction process. In addition,
aldehyde reactants with various groups are selected and used to discuss
the catalytic efficiencies of complex 1 to these reactants. Entries 3 and 4
exhibit that the catalytic yields are both significantly higher than 99%
because of the strong withdrawing groups of –F and –NO2 in the aldehyde
reactants to enhance the reaction efficiency [48–50]. However, the
3.4. Luminescent sensing properties
As illustrated in Fig. 5a and b, the luminescent spectrum of isolated
HL–OH ligand and prepared 2 were both discussed and measured in detail
at indoor temperature. The organic linker and 2 both displayed the
strongest emission peaks at 515 and 516 nm under the excitation light at
358 nm, respectively. The results illustrated that the luminescent property
of complex 2 comes from HL–OH ligand and is similar with that of the free
organic ligand. Taking into consider of the luminescent property of com-
plex 2, it encouraged us to investigate sample 2 as a sensing material to
detect metal ions. As shown in Fig. 5c and d, the emission intensities of 2
are collected in different organic solvents at room temperature, including
N, N-dimethylformamide (DMF), tetrahydrofuran (THF), acetonitrile
(MeCN), dichloromethane (CH2Cl2), acetone, tolune, methanol (MeOH),
and ethanol (EtOH); meanwhile, as-synthesized 2 can well keep its origin
luminescent intensity and position in DMF for 1 day. Therefore, all
detectable tests were measured and studied directly in DMF.
5

X. Zhang et al.
Journal of Solid State Chemistry 278 (2019) 120927
Fig. 6. (a) Emission spectra of complex 2 in DMF solution with different metal cations; (b) the relationship between emission intensities of 2 and Fe3þ concentrations;
(c) the Stern-Volmer plots of complex 2 for Fe3þ; and (d) the selective experiment for Fe3þ in the present of other interfering metal cations.
Fig. 7. (a) Reproducibility of ground 2 for Fe3þ at 3.5 ꢂ 10ꢁ4 mol Lꢁ1; (b) luminescent response for Fe3þ at different time intervals; (c) UV–Vis adsorption spectra of
selected metal cations; and (d) the PXRD profile of ground 2 after reusing four times.
6

X. Zhang et al.
Journal of Solid State Chemistry 278 (2019) 120927
Luminescent sensing efficiencies of ground 2 were collected detaily
References
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4. Conclusion
In conclusion, two PbII-based complexes were successfully designed
and constructed by tuning –NH2 and –OH substituting effect in the
organic linkers. Complex 1 is a good heterogeneous catalyst for Knoe-
venagel condensation reaction. Furthermore, complex 2 can be used as a
fast response and high selective sensor material for Fe3þ in DMF solution
with Ksv value as high as ~1.4 ꢂ 104 Mꢁ1. Meanwhile, they both have
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work provides a systematic research to design and tune coordination
complexes with their potential applications.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://do
i.org/10.1016/j.jssc.2019.120927.
7

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