Cu(I) coordination polymer based on pyridyl-functionalized resorcin[4]arene: Selective detection of Cr2O72?, MnO4? and nitrobenzene and efficient catalyst for azide–alkyne cycloaddition reaction

Article abstract of DOI:10.1016/j.poly.2018.11.032

In this work, a novel Cu(I) coordination polymer, Cu₂LBr₂ (1) based on a pyridyl-functionalized resorcin[4]arene [L = (2,8,14,20-tetraethyl-4,10,16,22-tetra kis((2-pyridylmethylene)oxy)-6,12,18,24-tetramethoxy-resorcin[4]arene)] has

Full text of DOI:10.1016/j.poly.2018.11.032

Accepted Manuscript
Cu(I) coordination polymer based on pyridyl-functionalized resorcinarene: se-
-
lective detection of Cr2O7 2-, MnO4 and nitrobenzene and efficient catalyst for
azide-alkyne cycloaddition reaction
Yan-Li Liu, Lei Yan, Ying-Ying Liu, Guo-Hai Xu, Wen-Jing Shi, Jian-Fang Ma
PII:
S0277-5387(18)30757-5
https://doi.org/10.1016/j.poly.2018.11.032
POLY 13579
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
2 October 2018
11 November 2018
Please cite this article as: Y-L. Liu, L. Yan, Y-Y. Liu, G-H. Xu, W-J. Shi, J-F. Ma, Cu(I) coordination polymer
-
based on pyridyl-functionalized resorcinarene: selective detection of Cr2O7 2-, MnO4 and nitrobenzene and efficient
catalyst for azide-alkyne cycloaddition reaction, Polyhedron (2018), doi: https://doi.org/10.1016/j.poly.2018.11.032
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Cu(I) coordination polymer based on pyridyl-functionalized
2-
resorcin[4]arene: selective detection of Cr2O7 , MnO4ˉ and
nitrobenzene and efficient catalyst for azide-alkyne cycloaddition
reaction
Yan-Li Liu,a Lei Yan,b Ying-Ying Liu,a,* Guo-Hai Xu,c,* Wen-Jing Shi,d and
Jian-Fang Ma,a,*
aKey Lab of Polyoxometalate Science, Department of Chemistry, Northeast Normal
University, Changchun 130024, P. R. China
bSchool of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024,
China
cKey Laboratory of Jiangxi University for Functional Materials Chemistry, School of
Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou, Jiangxi
341000, China
dSchool of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou
510006, China
* Correspondence authors
E-mail: liuyy147@nenu.edu.cn
E-mail: xugh308@gnnu.cn
E-mail: majf247@nenu.edu.cn
Fax: +86-431-85098620 (J.-F. Ma)
ABSTRACT
In this work, a novel Cu(I) coordination polymer, Cu2LBr2 (1) based on a
pyridyl-functionalized resorcin[4]arene [L = (2,8,14,20-tetraethyl-4,10,16,22-tetra

kis((2-pyridylmethylene)oxy)-6,12,18,24-tetramethoxy-resorcin[4]arene)] has been
synthesized under solvothermal condition. 1 was characterized by various
physicochemical analyses and it shows a ribbon structure. Notably, 1 exhibits an
outstanding thermal stability. 1 possesses strong luminescent property, and can
2-
selectively probe Cr2O7 , MnO4ˉ and nitrobenzene via luminescent quenching. In
addition, 1 is an efficient catalyst for azide-alkyne cycloaddition reaction.
Keywords: Copper(I), Resorcin[4]arene, Coordination polymer, Luminescence,
Azide–alkyne cycloaddition
1. Introduction
Resorcin[4]arenes have emerged as a kind of excellent organic hosts with
bowl-shaped cavities, and their rims could be modified by various functional groups
[1,2]. Coordination polymers (CPs) based on resorcin[4]arene have aroused interest
because of fascinating structures and diverse applications [3,4].
CPs as an important class of substances have been used in comprehensive fields
such as gas adsorption, catalysis, luminescene, drug delivery, and so on [5-9]. In this
respect, CPs-based luminescent quenching has drawn attention due to its selectivity,
2-
sensitivity and convenience [10,11]. It is well known that Cr2O7 and MnO4ˉ are
2-
common and important oxidants in both laboratory and industry [12]. Cr2O7 anion
has caused serious pollution towards ecological environment and threatened the
survival of various creatures because of its widely usage [13,14]. Also, nitrobenzene
(NB) as one of the poisonous organic pollutants has been utilized extensively in dyes,
anilines, explosives and pesticides [15,16]. Although a few multiple analytes have
been reported to probe their existence, it is still pressing to explore and develop new
efficient sensor [17-19].
CPs as heterogeneous catalysts possess many advantages compared to
conventional homogeneous catalysts, such as selectivity, easy separation, and high
catalytic performance [20,21]. Azide–alkyne cycloaddition (AAC) known as “click”
reaction can be catalyzed via Cu(I)-CPs to generate 1,4-disubstituted 1,2,3-triazoles
[22]. Much attention has been paid to this reaction owing to its inherent advantages

such as procedural simplicity, high selectivity and ultrahigh conversion [23]. In this
regard, various Cu(I)-CPs have been explored as effective catalysts with perfect yields
and regioselectivity for AAC reactions [24-26].
In view of the luminescent and catalytic properties, a Cu(I)-based CP, Cu2LBr2
(1), was achieved by
a
novel pyridyl-functionalized resorcin[4]arene
(2,8,14,20-tetraethyl-4,10,16,22-tetrakis((2-pyridylmethylene)oxy)-6,12,18,24-tetram
ethoxy-resorcin[4]arene) (L). Its structure was judged by crystallographic data and a
series of physical characterizations. It is worth noting that 1 can be used as
2-
luminescent sensor to detect Cr2O7 , MnO4ˉ and NB with high selectivity.
Furthermore, 1 shows excellent catalytic activities for AAC reaction.
Scheme 1. Synthetic route of L.
2. Experimental
2.1. Materials and instruments
IR spectra were gained by an Alpha Centaurt FT/IR spectrophotometer. TGA was
measured by a Perkin-Elmer TG-7 analyzer at a rate of 10 °C/min under N2
atmosphere. PXRD patterns were performed on a Rigaku Dmax 2000 X-ray
diffractometer with Cu-Kα radiation (λ = 0.154 nm). The catalytic yields of AAC
reaction were confirmed via GC equipment which is equipped with a FID detector
(GC-2014C, Shimadzu, Japan) and a capillary (30 m × 0.25 mm, WondaCAP 17). 1H
NMR spectra were determined in CDCl3 on a Bruker 600 MHz. The luminescent data
were collected by an Edinburgh FLSP920 fluorescence spectrometer, with Xenon
flash lamp, scan slit of 1.00 nm, Dwell time of 0.10 s and step of 1.00 nm. Solid state
UV–vis absorption spectra were obtained by a Cary 500 spectrophotometer. The
morphology was gained by a HITACHI SU8010 scanning electron microscope.
2.2. X-ray crystallography

Crystallographic data of 1 was collected by an Oxford Diffraction Gemini R CCD
diffractometer using Mo-Kα radiation (λ = 0.71073 Å). The refinement of the
structure was solved by the method of full-matrix least-squares using SHELXL-2013
program. The elaborate crystal data were listed in Tables 1 and 2.
2.3. Synthesis of L
The intermediate A (2,8,14,20-tetra-ethyl-4,10,16,22-tetra-hydroxy-6,12,18,24-
tetra-methoxy-resorcin[4]arene) was prepared according to previous report [27]. The
mixture of A (5.60 g, 8.52 mmol), K2CO3 (14.62 g, 0.106 mol) and 500 mL
acetonitrile was stirred for 0.5 h at rt. After that, 2-picolyl chloride hydrochloride
(8.69 g, 0.053 mol) was added into the mixture gradually. The reactive solution was
heated to reflux for 30 h under N2 atmosphere. The solvent was removed by rotary
evaporation and the obtained solid was washed by water. The white solid was
recrystallized with CH2Cl2 and MeOH and then dried (yield = 89.65%) (Scheme 1).
IR (cm-1): 3669 (w), 3063 (w), 2959 (m), 2931 (m), 2832 (w), 1608 (m), 1591 (s),
1496 (s), 1444 (m), 1375 (w), 1302 (s), 1197 (s), 1160 (m), 1122 (s), 1049 (m), 814
(w), 755 (m), 401 (w) (Fig. S1).
2.4. Synthesis of Cu2LBr2(1)
CuBr2 (8 mg, 0.036 mmol), L (10 mg, 0.01 mmol) and water/MeOH (6/2 mL) was
sealed in a 15 mL reactor and the temperature was kept at 160°C for 24 h. Then it was
slowly cooled to ambient temperature. The afforded yellow rod crystals of 1 were
washed with water/methanol (3:1 V/V) thoroughly and air-dried (based on L yield:
54%). Anal. Calcd for C64H68N4O8Cu2Br2: C, 58.71; H, 5.19; N, 4.28. Found: C,
58.53; H, 5.39; N, 4.36. IR (cm-1): 3068 (w), 2958 (m), 2830 (w), 1507 (s), 1436 (m),
1385 (m), 1299 (s), 1197 (s), 1123 (m), 1047 (m), 810 (w), 766 (w), 520 (w), 414(w).
2.5. Procedure of luminescent sensing
Ground 1 (3 mg) was immersed in 3 mL various aqueous solutions containing
different anions or organic solvents respectively. The mixtures were treated via
ultrasonic agitation to yield suspensions. The luminescent intensities were detected by
using the acquired suspensions.
2.6. Procedure for AAC reaction
In a 15 mL pressure-proof pipe, alkynes (2 mmol), azides (1 mmol), 1 (10 mg,
0.0076 mmol), amyl acetate (0.92 mmol) and MeOH (4 mL) were added. The

obtained mixture was stirred at 80°C for 12 h. Herein, amyl acetate was used as
internal standard reagent. The products of the catalytic reactions were confirmed by
1H NMR (Fig. S6). The final conversions were calculated by GC (Figs. S7 and S8).
Table 1. Crystallographic data of 1.
Formula
Mr
C64H68Br2Cu2N4O8
1308.12
Monoclinic
C2/c
Crystal system
Space group
a(Å)
25.385 (2)
16.408 (17)
18.629 (2)
90
b(Å)
c(Å)
α(°)
β(°)
130.593 (10)
90
γ(°)
V(Å3)
5892 (1)
4
Z
T(K)
293
Dcalc (g cm-3)
F(000)
Rint
1.475
2688
0.0626
GOF on F2
0.989
a
R1 [I>2σ(I)]
0.0634
b
wR2 (all data)
0.0986
2
2 2
aR1 = Σ||Fo| - |Fc||/Σ|Fo|. bwR2 = {Σ[w(Fo -Fc2)2]/Σw(Fo ) ]}1/2.
Table 2. Selected bond distances (Å) and angles (deg) for 1.
Cu(1)-N(3)#1
Cu(1)-N(1)
2.084(4)
N(3)#1-Cu(1)-N(1)
N(3)#1-Cu(1)-Br(1)
N(1)-Cu(1)-Br(1)
N(3)#1-Cu(1)-Br(1)#2
N(1)-Cu(1)-Br(1)#2
103.74(15)
105.79(12)
125.69(12)
120.54(12)
97.97(12)
2.108(4)
Cu(1)-Br(1)
Cu(1)-Br(1)#2
2.5125(11)
2.5448(11)
Br(1)-Cu(1)-Br(1)#2 104.56(3)
Symmetry codes: #1 x, -y, z + 1/2, #2 -x, y, - z + 1/2.

3. Results and discussion
3.1. Crystal Structure of 1
The independent unit of 1 consists of one Cu(I) ion, half of L and one Brˉ anion.
Each Cu(I) coordinates with two pyridyl nitrogen atoms from two L ligands and two
Brˉ anions, developing a tetrahedral coordination geometry. All nitrogen atoms in L
are participating in the coordination (Fig. 1a). The orientations of the pyridyl rings in
L are different. Each Brˉ anion acts as a bridging node and connects two adjacent Cu(I)
ions to produce a di-Cu(I) unit. L ligands connect dinuclear units to form a ribbon (Fig.
1b).
(a)
(b)
Fig. 1. (a) Coordination spheres of Cu(I) and L (Symmetry codes: #1x, -y, z + 1/2; #2-x,
y, -z + 1/2). (b) View of the ribbon.
3.2. Thermal and Chemical Stability.
To explore the thermal stability, thermogravimetric measurement was conducted
(Fig. 2). For 1, no marked change before 304°C was detected. This implies its
superior thermal stability. After that, the framework began to collapse.

Fig. 2. TG curve of 1 recorded in N2 atmosphere.
In order to investigate the chemical stability, 1 (20 mg) was soaked in water
solutions (10 mL) with different pH values ranging from 2 to 13, and various organic
solvents (10 mL) including dichloromethane (DCM), acetonitrile (MeCN),
cyclohexane (CYH), dimethylforamide (DMF), acetone, methanol (MeOH) and
ethanol (EtOH) for 24 h, respectively. As depicted in Fig. 3, almost all of the PXRD
curves match well with the simulated one, except that there is an additional peak at 2θ
= 13.6º in several curves. This demonstrates that the frameworks remained unchanged
[28]. After filtering the above mixtures, three filtrates (treated by pH = 2, pH = 13 and
DCM) were selected to test the dissolubility of 1 by ICP. The Cu(I) contents are 33.06,
42.56 and 0 μg, respectively. The results showed that 1 has faint solubility in strong
acid or strong alkali solutions. The additional peaks in several PXRD curves may be
influenced by the solvation or the different interplanar orientation of the crystals.
Fig. 3. PXRD curves of 1 immersed in water solutions with different pH values (a),
and various organic solvents (b).

3.3. Luminescent property
As demonstrated in Fig. 4, L shows an emission at 447 nm (λex = 380 nm), which
is due to π*→n or π*→π transitions [29]. The stronger emission peak of 1 occurs at
576 nm (λex = 380 nm), which is red shifted by 129 nm with respect to L. According
to previous report, the emission of 1 is originated from the metal-to-ligand
charge-transfer [30]. The luminescent intensity of 1 displays an obvious increase over
L, which may be attributed to the reinforce of the rigidity of the coordination between
L and Cu(I) ions [31].
Fig. 4. Solid state luminescent spectra of L and 1.
The temperature-dependent emission spectrum of 1 is revealed under liquid
nitrogen. Along with the temperature rising from 90 to 290 K, the emission peaks
show a slight blue shift from 604 nm to 588 nm. Meanwhile, the emission intensities
decreased (Fig. S2). The increment of intensities under cryogenic condition is due to
reducing the loss of energy via nonradiative decay [32].
3.4. Sensing of Cr2O72- and MnO4ˉ
Considering the strong luminescent intensity of 1, its underlying application in
detecting anions was performed systematically. In this work, ground finely 1 (3 mg)
was soaked in 3 mL aqueous solutions including KnX (0.01 M, X = OHˉ, Brˉ, Clˉ, Iˉ,
2-
2-
2-
2-
SCNˉ, S2O8 , HCO3ˉ, SO4 , CO3 , Cr2O7 and MnO4ˉ). As illustrated in Fig. 5, the
2-
emissions of 1 are largely related to the anionic species. Apparently, Cr2O7 and
MnO4ˉ display obvious quenching compared to other anions.

Fig. 5. Emission spectra (a) and intensities (b) of 1 in various anionic aqueous
solutions (λex = 380 nm).
In order to measure the ability of anti-interference of 1 towards anions,
competitive experiment was operated by taking Cr2O72- as an example. Finely mulling
1 (3 mg) was immersed in a series of aqueous solutions containing Cr2O72- (0.005 M)
along with other anions (0.01 M) respectively. As illustrated in Fig. 6, the quenching
effect of Cr2O72- on 1 is still ultrahigh even though other anions are loaded. The
phenomenon signifies excellent anti-interferential detecting ability of 1 towards
2-
Cr2O7 .
Fig. 6. Luminescent intensities of 1 with addition of Cr2O72- and other anions (λex =
380 nm).
3.5. Sensing of NB.
Organic toxic pollutants spread in water resource due to their widely usage in
various fields [33]. Herein, 1 was utilized to detect small organic molecules via
luminescent property. Fully ground 1 (3 mg) was immersed in 3 mL pure organic

solvents (MeCN, MeOH, acetone, EtOH, 2-propanol (IPA), DMF, DCM, DMA or
NB). As depicted in Fig. 7，all luminescent intensities in various solvents except NB
reach up to great counts. That is, NB exhibits an obvious quenching effect.
Fig. 7. Emission spectra (a) and intensities (b) of 1 in different organic solvents.
To evaluate the anti-interference test of 1 for NB, the suspension of 1 (3 mg)
with NB (1.5 mL) was introduced into other organic solvents (1.5 mL). As depicted in
Fig. 8, the emission intensities of 1 in mixed solvents are much lower than those in
pure solvents. That is, the quenching selectivity of 1 on NB was not influenced by the
presence of other solvents.
Fig. 8. Luminescent intensities of 1 in mixed solvents consisting of equal NB and
other organic solvents.
In order to study the recyclable performance of 1 in quenching, the reusability
2-
tests of 1 were studied. After three runs of sensing Cr2O7 or NB, their quenching
efficiencies only decreased about 1% (Fig. S3), which imply that 1 processes an
excellent recyclability.
To analyse the mechanism of quenching, 1 (20 mg) was immersed in the aqueous
solutions of Cr2O72- (0.01 M, 20 mL) or NB (20 mL) for 24 h. Their main PXRD

peaks are identical to that of the simulated pattern, which illustrate that the basic
framework of 1 remains unchanged (Fig. S4). Then the solid state UV-vis spectra of L
and 1 were tested. There is an intensive absorption band from 200 to 475 nm for 1
2-
(Fig. S5). Strong absorptions could be observed for the solution of Cr2O7 (ranging
from 250 to 450 nm) and NB (ranging from 225 and 320 nm), which are within the
band scope of 1 [34]. Upon excitation, Cr2O72- or NB competes with 1 for absorption
energy, thus resulting in the luminescent quenching [35,36].
3.6. Catalytic performance
Cu(I)-CPs are fascinating not only for their luminescent properties, but also for
their catalytic effects in AAC reactions [37]. To optimize the reactive condition,
phenylacetylene and benzyl azide were conducted as the model substrates with
different loadings of 1 under diverse temperatures and solvents (Table 3, Fig. S7).
Under MeOH solvent and 80 °C, the conversions were elevated from 6% to 98% and
99% with increasing loadings of 1 from 0 to 10 and 15 mg for 12 h (entries 1-4).
Subsequently, the reactions were done at 40°C and 60°C with catalyst 1 (10 mg) to
identify the suitable temperature. Only 14% and 72% yields were obtained
respectively (entries 5-6). In order to explore the effects of solvents, the reactions
were operated in different organic solvents containing MeCN, DCM and EtOH. The
best yields of 98% compared to those in MeCN and DCM can be gained in MeOH
and EtOH (entries 7-9).
Table 3. The catalytic reactions of phenylacetylene and benzyl azide under different
conditions a.
entry
Catalyst Temperature
Solvent
MeOH
Yieldb
(%)
(mg)
0
(°C)
1
2
3
4
6%
5
88%
98%
99%
80
10
15

5
6
7
8
9
40
60
14%
72%
58%
64%
98%
10
MeCN
DCM
EtOH
80
aReactive conditions: phenylacetylene (204 mg, 2mmol), benzyl azide (133 mg, 1
b
mmol) and amyl acetate (120 mg, 0.92 mmol). Amyl acetate was used to calculate
the yield by GC.
Under the optimized condition (10 mg of 1, MeOH and 80°C), kinetic experiment
between phenylacetylene and benzyl azide was tested to trace the reactive progress.
As shown in Table 4 and Figs. S7 and S9, the yield increased rapidly to 90% after 8 h.
Then, it continued to rise slowly from 90% to 98% in the following 4 h.
Table 4. The effects of time on the catalytic reactions of benzyl azide and
phenylacetylene.
entry
Catalyst Temperature
Solvent
Time
(h)
2
Yield
(%)
(mg)
(°C)
1
2
3
4
5
36%
86%
90%
93%
98%
6
10
80
MeOH
8
10
12
The next study focused on the catalytic universality of 1. Under the optimal
condition (10 mg of 1, MeOH, 80°C and 12 h), the reactions between functionalized
benzyl azides and phenylacetylenes were studied (Table 5 and Fig. S8). For para- and
meta-CH3 substituted benzyl azide, slightly lower yields (90% and 94%) were gained
(entries 2-3). When benzyl azide was substituted by other functional groups (ortho-F,
meta-NO2 and para-CN), the conversion yields can reach to 99% or 98%, respectively
(entries 4-6). Several substituted phenylacetylenes (para-F, -Cl, -methyl and -methoxy)
were also tried to react with benzyl azide and all yields can reach up to 98% or 99%

(entries 7-10). The high yields of above experiments implied that 1 owns excellent
catalytic universality for AAC reaction.
Table 5. Catalytic reactions of benzyl azides and phenylacetylenes with various
functional groupsa.
entry
Azide
Alkyne
Product
Yield(%)
1
98%
2
3
4
90%
94%
99%
5
6
98%
98%
98%
99%
98%
98%
7
8
9
10
aReactive conditions: alkynes (2 mmol), azides (1 mmol), amyl acetate (0.92 mmol), 1
(10 mg, 0.0076 mmol) and methanol (4 mL) at 80℃for 12 hours.
As to the catalytic reaction of 1-benzyl-4-phenyl-1H-1,2,3-triazole, 1 shows a
higher yield in a more wider scope of substrates than those related CPs, such as
Cu3(BTC) (BTC
=
1,3,5-tricarboxybenzene) (yield
=
88%) [38] and
[(CuI)2{ArS(CH2)3SAr}2]n (Ar = 4-F-C6H4) (yield = 97%) [39]. As to
[CuBr(DAPTA)3] (DAPTA = 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane)
(99%) [40], 1 exhibits a similar yield under more milder condition. This illustrates

that 1 could be employed as a promising catalyst for AAC reaction.
On the basis of literatures [41,42], a possible route for AAC reaction by 1 is
proposed (Scheme 2). It is generally accepted that Cu(I) ion attacks the alkyne, the
coordination intermediate A reinforces the acidity of terminal alkynyl hydrogen,
which result in the generation of intermediate Cu(I)–acetylide B. Then, N5 and N3
atoms in azide attack the electrophilic Cu(I) and C2 atoms in B to give a
six-membered Cu(I)-cycle C. Meanwhile, the metallacycle undergoes ring
rearrangement to yield D. After that, with the break of Cu–C bond and the protonation
of intermediate triazole, the product E and the catalyst 1 are formed.
Scheme 2. Proposed mechanism for AAC reaction by 1.
4. Conclusions
In brief, a novel Cu(I)-CP based on pyridyl-functionalized resorcin[4]arene has
been prepared successfully. 1 displays a charming ribbon structure. 1 possesses an
outstanding thermal stability. Systematical luminescent studies show that luminescent
intensities of 1 are closely related to the types of anions and organic solvents. 1 can be
2-
used to probe Cr2O7 , MnO4ˉ and NB with high selectivity. Remarkably, 1 can be
employed as an excellent catalyst for AAC reaction with high activity and yield. Thus,
1 shows promising applications in both luminescent sensing and catalyst.
Acknowledgments
This work was supported by the National Natural Science Foundation of China (Grant
No. 21471029 and 21761003). The Foundation for Distinguished Young Talents in

Higher Education of Guangdong (No. 2016KQNCX119). Scientific Research Project
of Guangzhou Municipal Colleges and Universities (No. 1201630192).
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In this work, a Cu(I) coordination polymer constructed by a novel
pyridyl-functionalized resorcin[4]arene and CuBr2 has been synthesized and
2-
structurally characterized. It can selectively detect Cr2O7 , MnO4ˉ and nitrobenzene
via luminescent quenching and effectively catalyse azide-alkyne cycloaddition
reaction.