A bi-functional 3D PbII–organic framework for Knoevenagel condensation reaction and highly selective luminescent sensing of Cr2O7 2?

Article abstract of DOI:10.1016/j.inoche.2019.04.042

A novel 3D Pb^II–organic framework {Pb(AIA)₂}_n (denoted as 1) can be successfully constructed by the assembly of 5-aminonicotinic acid (HAIA) and Pb^II cation under hydrothermal condition. The prepared 1 can be in

Full text of DOI:10.1016/j.inoche.2019.04.042

Accepted Manuscript
A bi-functional 3D PbII–organic framework for Knoevenagel
condensation reaction and highly selective luminescent sensing of
Cr2O72−
Miaochao Lin
PII:
S1387-7003(19)30352-1
DOI:
https://doi.org/10.1016/j.inoche.2019.04.042
INOCHE 7386
Reference:
To appear in:
Inorganic Chemistry Communications
Received date:
Revised date:
Accepted date:
8 April 2019
27 April 2019
27 April 2019
Please cite this article as: M. Lin, A bi-functional 3D PbII–organic framework for
Knoevenagel condensation reaction and highly selective luminescent sensing of Cr2O72−,
Inorganic Chemistry Communications, https://doi.org/10.1016/j.inoche.2019.04.042
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ACCEPTED MANUSCRIPT
1
II
A bi-functional 3D Pb –organic framework for Knoevenagel
condensation reaction and highly selective luminescent
2–
7
sensing of Cr O
2
a*
Miaochao Lin,
a
Department of Chemistry Chemical Engineering, Xinxiang University, Xinxiang
53003,China.
4
Corresponding Authors: Miaochao Lin
E-mail address: linmcxxu@sina.com

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2
Abstract
II
A novel 3D Pb –organic framework {Pb(AIA) } (denoted as 1) can be successfully
2
n
II
constructed by the assembly of 5-aminonicotinic acid (HAIA) and Pb cation under
hydrothermal condition. The prepared 1 can be investigated and characterized by
many technologies, including single-crystal X-ray diffraction, powder X-ray
diffraction, luminescent spectrum, elemental analysis (C, H, and N), UV-Vis spectrum,
as well as thermogravimetric analysis, respectively. The resultant 1 has lots of
uncoordinated pyridine nitrogen atoms and –NH in the structure, which can be
2
commonly considered as Lewis basic sites to catalysis Knoevenagel condensation
reaction. Meanwhile, the as-synthesized 1 with the luminescent property can be
2–
considered as a luminescent sensor for selective sensing of Cr O with excellent
2
7
recyclability at least reusing four runs.
II
Keywords: Pb –organic framework; catalysis; luminescent sensor; recyclability;
2
–
Cr O .
2
7
Materials are the most important and hot topic in our world, because they always
directly affect and change many research fields. Recently, metal–organic frameworks
[
1-4]
(namely MOFs)
have been developed and explored rapidly as a novel class of
inorganic-organic hybrid material by lots of material scientists and chemists, not only
[5-7]
because of their interesting and various constructions,
but also thanks to their
[
8-10]
[11-13]
extensive applications, including gas sorption/separation,
luminescent sensor,
[
14-16]
[17-19]
heterogeneous catalysis,
biological enzyme or drug loading,
and optical
[
20,21]
material.
Meanwhile, designability and controllability of MOFs directly promote
the booming development in all materials. Design and synthesis of novel MOFs with
targeted functional properties is still very important and interesting in this field,
attracting huge number of interests from many scientists. Actually, MOFs are crystal
materials and constructed by the coordination between metal cations and organic
[
22-24]
linkers.
Hence, MOFs can be fabricated by using different linkers, metal cations,
[
25-27]
and assemble conditions.
Among all application areas, heterogeneous catalysis

ACCEPTED MANUSCRIPT
3
and luminescent sensor both have been widely investigated for MOF materials due to
their important practical meanings and potential applications. Luminescent MOFs
with various luminescent sources have lots of superior properties for naked-eye
[
28-30]
visibility, fast response, high selectivity, and excellent recyclability.
As we know,
2
–
Cr O7 is a widely used and strong oxidant with high toxic and corrosive in the
2
2–
laboratory and industry. The excess of Cr O7 will significantly endanger human
2
being’s health and ecological environment, for example gastrointestinal problem,
ecological risk, cardiovascular failure, skin irritation, as well as respiratory
[
31,32]
infection.
Hence, it is important to design and prepare useful sensor materials to
2–
detect Cr O precisely for environmental conservation and health of human beings.
2
7
Furthermore, Knoevenagel condensation reaction is a classical organic synthesis
reaction, which is widely used in many industry fields and always applied to estimate
[
33,34]
the catalytic performance of catalysis.
In this work, we selected a rigid linker 5-aminonicotinic acid (denoted as HAIA),
II
which can be successfully assembled with Pb cation to construct a novel
three-dimensional (3D) framework {Pb(AIA) } (namely 1). The resultant crystals
2
n
were generated finally by heating HAIA, Pb(OAc) , and NaOH in MeCN at 120 °C
2
[
35]
for three days under hydrothermal synthesis. The achieved sample was studied by
single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), elemental analysis
of C, H, and N, thermogravimetric analysis (TGA), UV-Vis spectrum, and
luminescent property. Due to the luminescent property and various Lewis basic sites
(
uncoordinated pyridine nitrogen atoms and –NH ) in the structure, the resultant MOF
2
1
not only can be considered as Lewis basic catalyst for Knoevenagel condensation
reaction with good catalytic effect and recyclability, but also as a luminescent sensor
2–
toward Cr O with excellent selectivity and reusability.
2
7
Single-crystal X-ray diffraction result obviously shows that MOF 1 crystallizes in
[
36]
the triclinic crystal system and P–1 space group.
As depicted in Fig. 1a, the
II
asymmetric unit of as-synthesized 1 contains one independent Pb cation and two

ACCEPTED MANUSCRIPT
4
–
completely deprotonated AIA linkers. As shown in Figs. 1b and 1c, there are two
–
different coordination modes of AIA linker in MOF 1. The linker in mode I is
II
1
2
1
coordinated with three different Pb cations by  - :  :  ; meanwhile the linker in
3
II
1
1
1
mode II can be linked with three Pb cations as  - :  :  . The ration of mode I
3
and mode II is 1 : 1 in the whole structure. More interestingly, the free pyridine ring
exists in mode I, and uncoordinated –NH group retains in mode II, which both can be
2
considered as functional sites for the potential applications. As seen in Fig. 1d, the
II
coordination environment of Pb cation is seven-coordinated with five O-donors from
–
one bidentale and three monodentale carboxylic groups from four different AIA
–
bridging linkers, one –NH group and one pyridine ring from two AIA linkers (Pb–O
2
=
2.4452 – 2.7737 Å and Pb–N = 2.6407 – 2.7135 Å). In addition, two neighboring
II
Pb cations can be connected by each other through the carboxylic groups to construct
a bi-nuclear Pb cluster in Fig. 1d. The Pb···Pb distance in this cluster is about 3.1735
Å. Terminally, a novel 3D coordinated construction was successfully fabricated by the
II
coordinated force between these organic linkers and Pb centers (Figs. 1e-1g).

ACCEPTED MANUSCRIPT
5
Fig. 1. (a) The asymmetric unit of as-synthesized 1; (b and c) the coordination modes of bridging
II
organic linkers; (d) the coordination environment of Pb ; and (e-g) viewing of the 3D construction
of 1 (all hydrogen atoms are removed for clarity, and C, gray; N, blue; O, red; and Pb, green).
As shown in Fig. 2a, PXRD profile of as-synthesized MOF 1 was carefully
measured in air at room temperature. The data of experimental sample was consistent
with those of the simulated pattern from its single-crystal data, which clearly
illustrated that the prepared block samples are the same with the single-crystal
structure and pure phase. On the other hand, TGA data of the as-synthesized 1 was
measured in air from indoor temperature to 800 °C carefully. The results exhibited
that the framework can keep well to 300 °C, and a significant weight loss from 350°C
because of the organic linker decomposition (Fig. 2b).
Fig. 2. (a) PXRD data of simulated (black) and as-synthesized 1 (red); and (b) the corresponding
TGA data of fresh sample in air.
Due to various Lewis basic sites (uncoordinated pyridine nitrogen atoms and –NH2)
in MOF 1, the resultant sample can be investigated as an efficient basic catalyst.
Knoevenagel condensation reaction was studied in detail as a research model (Table
[
37-39]
1
1
).
Prior this reaction, experimental MOF 1 was immersed into fresh toluene for
2 hours and further dried in air. In this typical trial, substrate with different
functional groups (1 mmol), malononitrile (1.1 mmol), and catalyst (MOF 1, 100 mg)
with toluene (6 mL) were mixed together in a glass reactor. This mixture was directly
heated at a constant temperature at 85 °C for 4 hours in an oil bath. The finally yields

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6
can be easily made sure and calculated by the gas chromatography. All catalytic data
of these Knoevenagel condensation reactions with different aldehyde substrates were
summarized in Table 1. As seen in entry 1, the yield of the targeted product
2
-benzylidenemalononitrile product can reach up about 100%, which was further
selected as a reaction model to study the corresponding kinetic catalytic effect at
different reaction times (Fig. 3a). The obtained kinetic catalytic result obviously
displayed that the organic reaction almost reacted completely within 4 hours. To
investigate the necessary of catalyst 1, the reaction was stopped quickly after
removing 1. In addition, it is found that the catalytic yield was only about 6% without
catalyst 1 (entry 2). The above result evidently demonstrated that catalytic 1 plays a
significantly important role for this reaction. Furthermore, several substituted
aldehyde reactants were used to discuss and investigate the different performances in
the presence of MOF 1. As illustrated in entries 3 and 4, these corresponding catalytic
results shown that the excellent yields (>99%) were both founded for withdrawing
groups (–F and –NO ). However, the yields of aldehyde with electron-donor groups
2
decreased significantly. One –OMe group in entry 5 and two –OMe groups in entry 6
both decreased to 87 and 74, respectively. Due to the no-porous structure, the low
catalytic is not caused by the size diffusion or selectivity.
Table 1. All results of Knoevenagel condensation reactions based on different
aldehyde substrates.
O
CN
CN
CN
CN
+
R
H
R
Entry
1
Substrate
Product
Yield (%)
>99
O
CN
H
CN

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7
O
CN
CN
2
3
4
5
6
6
H
CN
CN
O
>99
>99
87
H
F
F
CN
O
H
CN
O2N
O2N
CN
O
CN
H
O
O
O
CN
CN
74
H
O
O
O
O
Notably, it is very important to easily recollect and regenerate for the
heterogeneous catalysis. For these reactions, MOF 1 can be feasibly separated and
-1
collected by simply centrifuging at 8500 rmin about 3 minutes, which can be further
regenerated after washing with fresh toluene. As founded in Fig. 3b, catalytic yields of
regenerated 1 after different runs were almost no any change in virtue of the stability
of MOF 1. The PXRD profile of MOF 1 after recycling four times clearly illustrated
that the whole network of MOF 1 can keep very well during the catalytic reaction in
Fig. S1.

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8
Fig. 3. (a) The kinetics analysis of Knovenagel condensation reaction; and (b) the reusability of 1.
As depicted in Fig. 4a, luminescent spectra of free HAIA linker and fresh sample 1
in solid state were both measured and collected at room temperature due to their
II
[40]
sensor applications of Pb -organic frameworks. The as-synthesized 1 has a broad
emission band at 395 nm under excitation 332 nm, which is very similar with that of
free linker (406 nm). It is obviously found that the maximum emission band of
as-synthesized 1 exhibits slight blue-shift performance compared with that of free
HAIA linker. According to the reported literatures, it may be mainly attributed to
II
enhancing the rigidity of bridging linker after coordinating to Pb cation to decrease
[
41]
the energy loss.
In virtue of MOF 1’s luminescence, we tried to investigate the
luminescent detection capability of 1. As seen in Fig. 4b, the luminescent intensities
of ground MOF 1 are significantly dependent on various solvent molecules. MOF 1
exhibits good luminescent property and insolubility in DMF; meanwhile, the
luminescent intensity can retain well even soaking in DMF for one day (Fig. 4c).
Hence, all luminescent sensing trials were measured and collected in DMF at room
temperature. More importantly, the recycled PXRD pattern of regenerated MOF 1 can
preserve its whole structure in DMF for one day (Fig. 4d).

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9
Fig. 4. (a) Solid-state luminescent spectra of free linker and as-synthesized 1; (b) luminescent
spectra of 1 in different solvents; (c) the emission intensity and (d) PXRD pattern of MOF 1 after
soaking in DMF for one day.
–
1
The ground crystals (1.0 mg L ) were ultrasonically dispersed in fresh DMF with
–
–
–
–
–
3
–
2–
4
2–
–4
–1
KX (X = F , Cl , Br , ClO , BrO , IO , CrO and Cr O , 5.0 × 10 mol L ),
3
3
2
7
which were collected their corresponding luminescent spectra after two minutes. The
results evidently exhibited that the luminescent intensities of ground MOF 1 were
–
–
–
–
–
–
2–
almost no changes in F , Cl , Br , ClO , BrO , IO , and CrO , while 1 happened
3
3
3
4
2–
obvious luminescent quenching performance in Cr O7 solution (Fig. 5a). It
2
2
7
–
obviously stated that MOF 1 is a greatly potential luminescence sensor to Cr O .
2
The titration experiments were implemented to quantitatively appraise the detection
2–
capability of MOF 1 toward Cr O in detail. As illustrated in Fig. 5b, the intensity of
2
7
2–
MOF 1 obviously reduced with the increasing Cr O7 concentration. As we know, the
2
detectability of sensors can be quantitatively calculated by the quenching constant
(
namely K ) from Stern-Volmer equation: (I /I) = K [M] + 1. [M] is the molar
sv 0 sv

ACCEPTED MANUSCRIPT
10
concentration of targeted analyte; meanwhile I and I are on behalf of luminescent
0
intensities of MOF 1 without and with analytes, respectively. As displayed in Fig. 5c,
4
–1
the calculated K value is about 1.14 × 10 M , which can be calculated by the value
sv
2–
of I /I – 1 and the concentration of Cr O in the low concentration range below 3.7 ×
0
2
7
–
5
–1
2
1
0 mol L with a good linear relationship R = 0.9945. Meanwhile, the calculated
detection limit can be calculated from 3δ/Slope (δ：standard error) and the detection
2
7
–
–5
–1
limit of Cr O is 1.03 × 10 mol L . Fig. 5d obviously shown that the luminescent
2
–
–
–
spectra of ground 1 can keep the original intensity in most of anions (F , Cl , Br ,
–
3
–
–
2–
ClO , BrO , IO , and CrO ), while the emission intensity could quench quickly
3
3
4
2
–
once adding Cr O in the above mixed solution. The experiments directly illustrated
2
7
2
–
that as-synthesized MOF 1 has the excellent selectivity for Cr O .
2
7
Fig. 5. (a) Luminescent spectra of 1 in different negative anions; (b) luminescent intensities of
2
7
–
MOF 1 at different concentrations of Cr O ; (c) Stern-Volmer plots and (d) selective experiments
2
2–
of 1 for Cr O7 in mixed negative anions.
2
Furthermore, the reusability of MOF 1 can be estimated by using recycle
experiments. Reused sample can be directly regenerated and recollected by

ACCEPTED MANUSCRIPT
11
centrifugation and washing with DMF several times. As illustrated in Fig. 6a, the
regenerated crystals keep their luminescent detection capability even reusing four runs.
2
–
The response rates of MOF 1 to Cr O7 can be monitored at different time intervals.
2
It is easily founded that ground 1 can fastly achieve the minimum intensity and
preserve for a long time, illustrating that the quenching performance is not caused by
guest capture (Fig. 6b). From UV-Vis absorption spectra of these chosen negative
2–
anions, it shown that only Cr O anion has an obviously overlap with the excitation
2
7
spectrum of MOF 1 (Fig. 6c). Hence, the quenching mechanism may be possibly
2– [42,43]
ascribed to the excitation energy competitive between MOF 1 and Cr O .
In
2
7
addition, the PXRD result of sample 1 after continuously using four runs proved that
the entire network can be kept well for the sensor process (Fig. 6d). Furthermore, the
FT-IR spectra of reused samples after four times are consisting with the fresh sample
to prove the structural stability (Fig. S2).
2–
–4
–1
Fig. 6. (a) Reusability of 1 for Cr O7 (5.0 × 10 mol L ); (b) luminescent response rates of 1
2
2–
toward Cr O7 at different time intervals; (c) UV-Vis spectra for the selected anions; and (d) the
2

ACCEPTED MANUSCRIPT
12
PXRD profile of 1 after reusing four runs.
II
In conclusion, a 3D Pb –organic framework can be successfully constructed based
on HAIA linker under hydrothermal condition, which has lots of uncoordinated
pyridine nitrogen atoms and –NH in the structure to use as a Lewis basic catalyst to
2
catalysis Knoevenagel condensation reaction. Meanwhile, as-synthesized 1 can be
2–
considered as a luminescent sensor for Cr O7 with excellent selectivity. In addition,
2
as-synthesized 1 has outstanding reusability at least four runs.
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II
Significant gas adsorption and catalytic performance by a robust Cu -MOF
derived through single-crystal to single-crystal transmetalation of a thermally
II
less-stable Zn -MOF, Chem. Eur. J. 21 (2015) 19064–19070.
[
35]Synthesis of {Pb(AIA) } (1): A mixture of Pb(OAc) (0.1 mmol), HAIA (0.18
2
n
2
mmol), and 0.2 mL of LiOH (0.1 M) was dissolved in CH CN (2.5 mL) and H O
3
2
(1.75 mL), which was continuously heated at 125 ºC for 2 days in a Teflon-lined
stainless steel vessel under autogenous pressure. The mixture was slowly cooled
to indoor temperature. The block single crystals were directly collected and
washed by fresh MeCN, which was dried in air with 59% yield based on
Pb(OAc) . Anal. Calcd for C H O N Pb: C, 30.0; H, 2.1; N, 11.6 %. Found: C,
2
12 10
4
4
2
9.9; H, 2.0; N, 11.7 %.
[
36]Crystal data of C H O N Pb: F = 646.9(2), triclinic, P–1, a = 6.6657(12), b =
12 10 4 4 w
8
6
2
.7149(15), c = 11.368(2) Å, α = 93.503(3), β = 100.069(2), γ = 93.963(2) °, V =
3
-3
–1
46.9(2) Å , Z = 2, Dc = 2.472 g cm , μ = 13.064 mm , R(int) = 0.0132, Nref =
982, R = 0.0202, wR = 0.0500 [I > 2σ(I)], R = 0.0214, wR = 0.0505 [all data],
1
2
1
2
2
Goodness-of-fit on F = 1.038. Large single crystal data for MOF 1 was directly
collected on a Bruker SMART CCD diffractometer based on a graphite
monochromated Mo K (λ = 0.71073 Å) at room temperature. The crystal
α
structures were successfully analysed and refined using a direct and full-matrix
2
least squares method on F with anisotropic thermal parameters for
[
44,45]
[46]
non-hydrogenatoms (SHELXL-2015)
through OLEX2 interface program
.
[
[
37]W. Jiang, J. Yang, Y.-Y. Liu, S.-Y. Song, J.-F. Ma, A stable porphyrin-based
porous mog metal–organic framework as an efficient solvent-free catalyst for
C–C bond formation, Inorg. Chem. 56 (2017) 3036–3043.
38]Y. Zhang, Y. Wang, L. Liu, N. Wei, M.-L. Gao, D. Zhao, Z.-B. Han, Robust
bifunctional lanthanide cluster based metal–organic frameworks (MOFs) for
tandem Deacetalization–Knoevenagel reaction, Inorg. Chem. 57 (2018)
2
193–2198.
[
39]X.-S. Wang, J. Liang, L. Li, Z.-J. Lin, P. P. Bag, S.-Y. Gao, Y.-B. Huang, R. Cao,
An anion metal–organic framework with Lewis basic sites-rich toward

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charge-exclusive cationic dyes separation and size-selective catalytic reaction,
Inorg. Chem. 55 (2016) 2641–2649.
[
[
40]X. Luo, X. Zhang, Y. Duan, X. Wang, J. Zhao, A novel luminescent
Pb(II)-organic framework exhibiting a rapid and selective detection of trace
3
+
amounts of NACs and Fe with excellent recyclability, Dalton Trans. 46 (2017)
303–6311.
6
41]F. Guo, Z. Chu, M. Zhao, B. Zhu, X. Zhang, Anion-templated assembly of three
metal-organic frameworks with diverse structures for highly selective detection of
2
7
−
3+
Cr O and Fe in aqueous solution, J. Solid State Chem. 274 (2019) 92–99.
2
[
[
42]S.-F. Tang, X. Hou, A highly stable dual functional zinc phosphite carboxylate as
3
+
2–
luminescent sensor of Fe and Cr O , Cryst. Growth Des. 19 (2019) 45–48.
2
7
43]J.-X. Li, D. Liu, Z.-C. Hao, G.-H. Cui, An unusual (3,4,5)-connected 3D
cadmium metal–organic framework as a luminescent sensor for detection of
2
7
−
Cr O in water, Inorg. Chem. Commun. 97 (2018) 79–82.
2
[
[
44]G. M. Sheldrick, A short history of SHELX, Acta Cryst. A 64 (2008) 112–122.
45]G. M. Sheldrick, Crystal Structure Refinement with SHELXL, ActaCryst. C 71
(2015) 3–8.
[
46]O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program, J. Appl.
Cryst. 42 (2009) 339–341.

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Graphical Abstract-Pictogram
II
This work presents a bi-functional 3D Pb –organic framework for Knoevenagel
2
–
condensation reaction and highly selective luminescent sensing of Cr O . In
2
7
addition, the resultant sample has excellent recyclability.

ACCEPTED MANUSCRIPT
19
Highlights
II
1
2
3
. A bi-functional 3D Pb -based MOF is successfully constructed.
. It is an excellent catalysis for Knoevenagel condensation reaction.
2
-
. It exhibits outstandingly selective luminescent sensing toward Cr O .
2
7