Three thiacalix[4]arene-based Cu(i) coordination polymers: Catalytic activities for azide-alkyne cycloaddition reactions and luminescence properties

Article abstract of DOI:10.1039/c9dt03060c

Three new coordination polymers, [Cu₂(CN)(L)(OCH₃)]·CH₃OH·3H₂O (1), [Cu₃(Br)₃(L)] (2) and [Cu(I)(L)]·1.5H₂O (3), have been solvothermally prepared by reacting L (5,11,17,23-tetra

Full text of DOI:10.1039/c9dt03060c

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Three thiacalix[4]arene-based Cu(I) coordination
polymers: catalytic activities for azide–alkyne
Cite this: DOI: 10.1039/c9dt03060c
cycloaddition reactions and luminescence
properties†
a
Jian-Fang Li,a Peng Du,b Ying-Ying Liu,*a Guo-Hai Xu*c and Jian-Fang Ma
*
Three new coordination polymers, [Cu2(CN)(L)(OCH3)]·CH3OH·3H2O (1), [Cu3(Br)3(L)] (2) and [Cu(I)
(L)]·1.5H2O (3), have been solvothermally prepared by reacting L (5,11,17,23-tetra-tert-butyl-25,26,27,28-
tetra[(3-pyridylmethyl)oxy]-2,8,14,20-tetrathiacalix[4]arene) with Cu(I) halide. 1 and 2 exhibit layers. 3 dis-
plays a chain, a supramolecular layer constructed by hydrogen bonds. The performance of 1–3 was
examined as heterogeneous catalysts for azide–alkyne cycloaddition reactions. Most strikingly, 1 and 2
show predominant efficiency with high regioselectivity and excellent recyclability. Remarkably, solids 1–3
all have luminescence characteristics under irradiation with a UV lamp.
Received 26th July 2019,
Accepted 12th September 2019
DOI: 10.1039/c9dt03060c
rsc.li/dalton
disadvantages of homogeneous catalysts such as easy destruc-
1. Introduction
tion and difficult recycling.11,16,17
Recently, Cu(I)-based coordination polymers (CPs) have
Thiacalix[4]arenes have been proved to be versatile building
attracted wide attention because of their good stabilities and blocks owing to their multidentate coordination sites and
fascinating catalytic activities in reactions including the con- cavity structures.18 The upper p-tert-butyl and the lower pheno-
version of arylalkanes to ketones,1 azide–alkyne cycloaddition lic hydrogen atoms of the backbone could be replaced by
(AAC) reactions,2 sequential alkynylation and cycloaddition various substituents, and a series of derivatives based on thia-
reactions3 and carbonyl–olefin photocycloaddition reactions.4 calix[4]arenes have been synthesized.19–22 Based on functiona-
AAC reaction is a highly economical method for the synthesis lized thiacalix[4]arene ligands, plenty of CPs with intriguing
of 1,2,3-triazole derivatives by cycloaddition of alkynes with structures and unique properties have been reported.23–30 Our
azides.5 This reaction has applications in various fields such group has been engaged in the exploration of CPs based on
as organic synthesis, polymer chemistry, materials science and this type of ligand.31 To expand our research, we synthesized
drug discovery.6–8 Focusing on AAC reactions, a lot of catalytic
a pyridyl-functionalized p-tert-butylthiacalix[4]arene ligand
studies have been carried out. Pioneering research suggests 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra[(3-pyridylmethyl)oxy]-
that nickel-, iridium-, silver- and copper-based salts or com- 2,8,14,20-tetrathiacalix[4]arene (L, Scheme 1). The ligand may
pounds show fascinating catalytic activities.9–11 In this regard, be a good backbone for the construction of CPs, because the N
copper-catalyzed AACs are the most efficient reactions, and a
few Cu(I)-CPs have been studied as catalysts owing to their
heterogeneous catalytic features.12–15 They can overcome the
aKey Lab of Polyoxometalate Science, Department of Chemistry, Northeast Normal
University, Changchun 130024, China. E-mail: liuyy147@nenu.edu.cn,
majf247@nenu.edu.cn
bCollege of Chemistry and Chemical Engineering, Dezhou University, Dezhou
253023, China
cKey Laboratory of Jiangxi University for Functional Materials Chemistry, School of
Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou, Jiangxi
341000, China. E-mail: xugh308@gnnu.cn
†Electronic supplementary information (ESI) available. CCDC 1943377–1943379.
For ESI and crystallographic data in CIF or other electronic format see DOI:
10.1039/C9DT03060C
Scheme 1 View of L.
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and the S atoms can provide multiple potential sites to coordi- C64H68Cu3Br3N4O4S4: C, 50.71; H, 4.52; and N, 3.70. Found (%):
nate with metal ions. Also, the pyridyl groups can freely rotate C, 50.55; H, 4.37; and N, 3.91. IR (cm−1): 3446 (m), 3046 (m),
during coordination.
2963 (s), 2867 (s), 1773 (w), 1598 (m), 1578 (m), 1476 (s),
In this work, we first carried out the systematic investi- 1460 (s), 1441 (s), 1378 (s), 1364 (s), 1322 (m), 1263 (s), 1225 (s),
gation of the reaction of L with Cu(I) halide and explored three 1124 (w), 1083 (s), 1021 (s), 972 (s), 942 (s), 873 (m), 849 (m),
new CPs, [Cu2(CN)(L)(OCH3)]·CH3OH·3H2O (1), [Cu3(Br)3(L)] 821 (w), 792 (s), 761 (m), 724 (m), 702 (s), 646 (m), 536 (w).
(2) and [Cu(I)(L)]·1.5H2O (3). Their catalytic properties for AAC
2.4. Preparation of [Cu(I)(L)]·1.5H2O (3)
reactions and luminescence properties have been discussed.
Meaningfully, 1 and 2 are recyclable heterogeneous catalysts
An admixture of
L (11 mg, 0.01 mmol), CuI (8 mg),
and display excellent catalytic capabilities for the AAC reaction. H3Mo12O40·xH2O (18 mg) and DMF/H2O (6/2 mL) was trans-
ferred to a 15 mL Teflon reactor and then kept at 110 °C for
72 h. The yield of colorless block crystals is 36%. Anal. calcd
2. Experimental section
2.1. Synthesis of L
(%) for C64H71CuIN4O5.5S4: C, 58.94; H, 5.44; and N, 4.29. Found
(%): C, 58.70; H, 5.38; and N, 4.53. IR (cm−1): 2959 (s), 2904 (m),
2867 (m), 1680 (m), 1478 (m), 1445 (s), 1424 (s), 1376 (s), 1264 (s),
1234 (m), 1085 (m), 1016 (m), 794 (m), 707 (m).
Ligand L was synthesized by similar procedures to those
reported in the literature.32,33
Crystallographic data are listed in Table 1.
2.2. Preparation of [Cu2(CN)(L)(OCH3)]·CH3OH·3H2O (1)
L (11 mg, 0.01 mmol), CuCl2·2H2O (8 mg, 0.04 mmol) and
NH4VO3 (6 mg, 0.06 mmol) in N,N-dimethylformamide (DMF)/
methanol (MeOH) (2/6 mL) were heated at 110 °C for 72 h in a
3. Results and discussion
3.1. Syntheses
15 mL Teflon reactor. After cooling, yellow-green block crystals For CPs 1 and 2, we tried the syntheses by using CuCl and
were obtained. The product ratio is 42% based on L. Anal. CuBr as well, but we only obtained powder forms. Since the
calcd (%) for C67H81Cu2N5O9S4: C, 59.35; H, 6.02; and N, 5.17. structures of 1 and 3 contain only L ligands without polyoxo-
Found (%): C, 59.38; H, 5.70; and N, 5.23. IR (cm−1): 3053 (w), metalates, their crystals could only be obtained by adding
2959 (s), 2903 (m), 2866 (m), 2122 (w), 1772 (w), 1677 (w), 1577 NH4VO3 and H3Mo12O40, respectively. The reason may be that
(m), 1541 (w), 1477 (m), 1443 (s), 1426 (s), 1375 (m), 1329 (w), they altered the pH values of the reaction solutions.
1264 (s), 1232 (m), 1085 (m), 1021 (m), 975 (m), 945 (m), 878 (m),
3.2. Crystal structure of [Cu2(CN)(L)(OCH3)]·CH3OH·3H2O (1)
850 (w), 761 (w), 794 (m), 703 (m), 646 (w), 536 (w) (Fig. S1†).
The structure of 1 was refined by using the SQUEEZE program
in PLATON and the disordered solvents were determined by
2.3. Preparation of [Cu3(Br)3(L)] (2)
L (11 mg, 0.01 mmol), CuBr2 (9 mg, 0.04 mmol) and DMF/ electron diffraction density analysis, elemental analysis and
EtOH (2/6 mL) were added in a 15 mL Teflon reactor and then TGA. The self-contained unit of 1 consists of one L, two Cu(I)
heated at 110 °C for three days. Yellow block crystals were cations, one CN− anion, one CH3O− anion, one free MeOH
obtained, and the yield is 73%. Anal. calcd (%) for and three free H2O molecules. The CN− anion comes from the
Table 1 Crystallographic data and structure refinements for 1–3
1
2
3
Formula
Mr
Crystal system
Space group
a (Å)
b (Å)
c (Å)
C67H81Cu2N5O9S4
1355.68
Triclinic
ˉ
P1
15.1320(8)
15.5740(8)
16.9320(8)
75.653(4)
82.818(4)
61.305(5)
3391.0(3)
2
C64H68Cu3Br3N4O4S4
1515.81
Triclinic
ˉ
P1
10.9843(7)
16.0778(11)
19.4622(10)
108.212(5)
91.375(4)
99.797(5)
3206.4(4)
2
C64H71CuIN4O5.5S4
1302.92
Triclinic
ˉ
P1
15.282(8)
15.561(8)
15.889(9)
105.876(5)
111.146(5)
90.496(4)
3365.3(3)
2
α (°)
β (°)
γ (°)
V (Å3)
Z
Dcalc (g cm−3
F(000)
)
1.328
1424
1.570
1536.0
1.286
1346.0
Rint
0.0390
1.138
0.1123
0.2464
0.0443
0.979
0.0533
0.1255
0.0339
1.062
0.0514
0.1333
GOF on F2
R1a [I > 2σ(I)]
wR2b (all data)
a R1 = Σ||Fo| − |Fc||/Σ|Fo|. b wR2 = {Σ[w(Fo2 − Fc2)2]/Σ[w(Fo2)2]}1/2
.
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Fig. 2 (a) Coordination spheres of Cu(I) ions in 2. (b) View of the
[Cu3(Br)3] cluster and the 2D layer.
surrounded by two N atoms of L ligands and two I− anions
(Fig. 3a). Two Cu(I) cations are held together by two I− anions
to form a [Cu2(I)2] dimer. As revealed in Fig. 3b, the dimers are
interconnected by L ligands to form a double chain. Only two
N atoms of L participate in the coordination. The chains are
further held together by C–H⋯N bonds among L ligands
(Table S2†), forming a supramolecular layer (Fig. 3c).
Fig. 1 (a) Coordination spheres of Cu(I) ions in 1. (b) View of the layer.
decomposition of DMF. The two Cu(I) cations show different
coordination modes: Cu1 exhibits a distorted tetrahedron and
is surrounded by three N atoms of three L ligands and one
CN− anion, while Cu2 is ligated by one N atom, one CN− anion
and one CH3O− anion (Fig. 1a). Rather than the cone confor-
mation in other thiacalix[4]arene CPs,34,35 L exhibits a 1,3-
alternate conformation, and all four N atoms participate in the
coordination. CN− anions further linked the Cu(I) ions and L
ligands to form a layer (Fig. 1b).
3.5. Chemical and thermal stability
To examine their chemical stability, CPs 1–3 (15 mg) were
immersed in various solvents (including acetone, dichloro-
methane (DCM), DMF, MeOH, EtOH, acetonitrile and ethyl
acetate) and aqueous solutions with various pH values for one
day, respectively. As shown in Fig. 4, the PXRD patterns of
immersed 2 are consistent with the simulated patterns. This
shows that 2 displays excellent stability in both organic sol-
vents and acid/base solutions with a wide range of pH values.
This high stability may be because the structure of 2 contains
no coordinated or free solvents. The PXRD patterns of
immersed 1 in DMF, acetone, and acid/base solutions show
minute shifts at 2θ = 5.3°, 6.7° and 9.6° compared with the
simulated patterns (Fig. S2†), which may be caused by the
changing of coordinated solvents. The PXRD patterns of
immersed 3 are not consistent with the simulated patterns,
indicating that the framework has changed.
3.3. Crystal structure of 2
The independent unit of 2 incorporates one L, three Cu(I) cations
and three Br− anions (Fig. 2a). The three Cu(I) cations have
different coordination environments. Each of the Cu1 and Cu2
cations are surrounded by two N atoms from L ligands and two
Br− anions. Cu3 is coordinated by two Br− anions. Cu1, Cu2 and
Cu3 are bridged by three Br− anions to form a [Cu3(Br)3] cluster.
Cu(2)⋯Cu(3) and Cu(1)⋯Cu(3)#2 distances are 2.7977(11) and
2.8041(11) Å, respectively (Table S1†). The [Cu3(Br)3] clusters are
connected by 1,3-alternate L ligands to afford a layer (Fig. 2b).
3.4. Crystal structure of 3
TGA of 1–3 was performed under nitrogen (Fig. S3†). For 1,
One Cu(I) cation, one L, one I− anion, and one and a half free a weight loss was observed in the range of 97–278 °C corres-
H2O molecules constitute the independent unit of 3. Cu1 is ponding to the loss of free CH3OH, H2O and coordinated
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CH3O− molecules. The framework of 2 began to collapse at
280 °C. The weight loss of 3 was observed at about 100 °C due
to the loss of the solvent molecules.
3.6. Catalytic performance of 1–3 in AAC reactions
Considering the Lewis acidic Cu(I) sites in CPs 1–3, AAC reac-
tion of benzyl azide and phenylacetylene was conducted
(Table 2 and Fig. S4†). Firstly, a blank experiment was carried
out, and only 13% yield was obtained (entry 1). To confirm the
active sites in the reactions, the halides of Cu(I) were utilized
as homogeneous catalysts, and low conversion yields were
achieved (33% and 35% for CuCl and CuI, entries 2 and 3). An
optimization experimental study was carried out with 2
because of its high yield during the synthesis. Firstly, to opti-
mize the solvents, the reactions were operated in MeOH, EtOH
and dichloromethane (DCM), respectively. A maximum yield of
>99% in MeOH and EtOH was obtained (entries 4–6). In order
to explore the reaction time, the process was monitored every
two hours. The yields were elevated from 66% to 86% and
97% at 2, 4 and 6 h, respectively (entries 7–9). Subsequently,
the reaction was done at 50 °C to identify the suitable tempera-
ture. Only 67% yield was obtained (entry 10). Under the
optimum conditions summarized in the above experiments,
the catalytic yields of 1 and 3 were found to be >99% and 34%,
respectively (entries 11 and 12).
In order to study the generalities of 1 and 2, diverse azides
and alkynes with different functional groups were studied
under the optimized conditions (Fig. S5 and S6†). When
4-CH3-, 3-CH3-, 2-F- and 4-NO2-substituted (azidomethyl)
benzene reacts with ethynylbenzene, yields of >99% and 97%
were obtained (entries 1–4 in Table 3). This demonstrates that
an electron-donating or -withdrawing group substituted (azido-
methyl)benzene has no effect on AAC reactions. However,
when (azidomethyl)benzene reacts with ethynylbenzene
derivatives, the yields are affected. As for the 4-CH3- and
4-OCH3-groups, the yields are 96% and 85%, respectively
(entries 5 and 6). For 4-Cl- and 4-Br-substituted groups, the
yields reduced to 65%, 63% and 60% for both 1 and 2 (entries
Fig. 3 (a) Coordination spheres of Cu(I) ions in 3. (b) View of the chain.
(c) View of the supramolecular layer (blue dots represent H bonds).
Fig. 4 The PXRD patterns of 2 immersed in different organic solvents and solutions with various pH values.
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Table 2 Optimization of reaction conditions for AAC reactions
Entry
Catalyst
Time, h
Solvent
Temperature, °C
Yield, %
1
2
3
4
5
6
7
8
None
CuCl
CuI
2
2
2
2
2
2
8
8
8
8
8
8
2
4
6
8
8
8
MeOH
MeOH
MeOH
MeOH
EtOH
70
70
70
70
70
70
70
70
70
50
70
70
13
33
35
>99
>99
90
66
86
97
67
>99
34
DCM
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
9
10
11
12
2
1
3
Reaction conditions: catalyst (10 mg), benzyl azide (1 mmol), phenylacetylene (2 mmol), solvent (4 mL), 8 h 70 °C and amyl acetate (0.92 mmol).
Table 3 Catalytic reactions of substrates with different functional groupsa
Yield, %
Entry
1
Azides
Alkynes
Product
1
2
>99
>99
2
3
>99
>99
>99
>99
4
5
>99
96
97
96
6
7
96
65
85
63
8
65
60
a Reaction conditions: azide (1 mmol), alkyne (2 mmol), amyl acetate (0.92 mmol), catalyst (10 mg) and methanol (4 mL) at 70 °C for 8 h.
7 and 8). This shows that ethynylbenzene with electron-with- group substituted ethynylbenzenes are low. The catalytic
drawing groups results in lower yields.36 According to the effects of 1 were obviously better than those of 2 for several
related literature, during the reaction pathway of substituted substituted ethynylbenzene reactions, which may be caused by
1,2,3-triazoles, an initial Cu(I)–acetylide intermediate is the higher porosity and more open Cu(I) sites of 1 than 2.11
formed by Cu(I)-CPs and alkynes.10 The alkynes with electron
Recyclability is crucial for catalytic reactions (Fig. S7 and
withdrawing groups tend to form dimers,36 which may S8†). So we conducted cycle experiments after the catalysts 1
decrease the formation of Cu(I)–acetylide intermediates. and 2 were removed from AAC reactions. Both catalysts could
Therefore, the yields obtained using electron-withdrawing be easily separated from the reaction systems by filtration.
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Fig. 5 The yields of cycle experiments catalyzed by 1 and 2.
After five cycles, the yields of the reactions catalyzed by 1 and 2
did not change significantly and the PXRD patterns of 1 and 2
were nearly consistent with their simulated patterns
(Fig. 5 and S9†). This demonstrates that the structural integri-
ties of 1 and 2 are well preserved.
To investigate whether the catalysis is a heterogeneous reac-
tion, the catalysts were separated from the reaction systems by
hot filtration after 2 h (Fig. 6). Even after continuing the reac-
tions with filtrates for 6 h, there was no significant increase in
yields for both CPs. The results show that 1 and 2 act as
heterogeneous catalysts in AAC reactions.
Table 4 Comparison of cycloaddition of benzyl azide and phenyl-
acetylene by various catalysts
Catalyst
Conditions
Yield, %
Ref.
[Cu6I6(L1)2]n
[CuCl2(L2)2]
[Cu(dmph)2]Cl
[Cu(tzol)2]
CuL2
Cu(BTC)-MOF
CP 1
24 h/MeOH + H2O/50 °C
15 h/MeOH + H2O/35 °C
12 h/H2O/70 °C
12 h/H2O/70 °C
12 h/H2O/70 °C
16 h/MeOH/50 °C
8 h/MeOH/70 °C
8 h/MeOH/70 °C
100
99
97
96
95
81
>99
>99
37
38
39
40
41
42
This work
This work
CP 2
The catalytic performance of the CPs prepared in this work
has been compared with the reported CP-catalysts for AAC
reaction of benzyl azide and phenylacetylene. As shown in
Table 4, 1 and 2 exhibit approximate or higher catalytic
efficiencies. The advantage of this work lies in the shorter reac-
tion time.37–42 Another advantage of 1 and 2 is that they have
excellent recyclabilities.37,38,42
3.7. Luminescence properties
The solid-state luminescence features of 1–3 and L were evalu-
ated at RT. As illustrated in Fig. 7, the emission of 1 led to red
light with a peak value of 633 nm (λex = 363 nm). 2 and 3 show
green luminescence with the maximum peaks at 548 nm (λex
=
389 nm) and 526 nm (λex = 400 nm), respectively. The green-
light of 2 and 3 may be caused by the short distances of
Cu⋯Cu (2.670–2.804 Å) (Table S1†) and halogen-to-metal
charge transfer (XMCT).43 Compared with the L ligand (λem
=
Fig. 7 Solid state luminescence spectra of 1–3.
Fig. 6 Hot filtration experiments catalyzed by 1 and 2 after 2 h.
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565 nm, yellow light, Fig. S10†), 1 displays an obvious red shift
of 68 nm, which could be ascribed to MLCT.44,45
To investigate the effect of temperature on luminescence,
different-temperature emissions of 1–3 were studied at 97 K,
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sion intensities decreased with increasing temperature
(Fig. S11†), which may be caused by the increasing loss of
energy via nonradiative decay.46
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4. Conclusions
In conclusion, three new Cu(I)-CPs constituted by CuCl2,
CuBr2, CuI and a pyridyl-functionalized p-tert-thiacalix[4]arene
ligand have been prepared. The study represents the first
example of Cu(I)-halide CPs bearing the L ligand. 1 and 2
exhibit layer structures, and 3 displays a double chain. 2 has
good chemical and thermal stability. Strikingly, 1 and 2 can
efficiently catalyze AAC reactions. They can also be easily separ-
ated from their reaction systems. After cycling, the activities of
1 and 2 exhibited no obvious decreases and their integrities
were maintained. High stability, easy separation, high catalytic
ability and reusability make CPs 1 and 2 excellent hetero-
geneous catalysts for the AAC reactions. The solid-state lumine-
scence spectra indicate that 1–3 exhibit red or green
emissions.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the NSFC (Grant No. 21771034
and 21761003).
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