Construction of four copper coordination polymers derived from a tetra-pyridyl-functionalized Calix[4]arene: Synthesis, structural diversity, and catalytic applications in the A3 (Aldehyde, Alkyne, and Amine) coupling reaction

Article abstract of DOI:10.1021/acs.cgd.7b00898

Solvothermal reactions of CuX₂ (X = NO₃, Cl, Br, I) with tetra-pyridyl-functionalized calix[4]arene at 130 °C afforded four novel coordination polymers, {[(CuNO₃)₂L]·MeOH}_n (1), [(CuCl₂)-L_0.5]_n (2), [(Cu₃Br₃)L]_n (3), and [(Cu₃I₃)L]_n (4), where L = 25,26,27,28-tetra[(3-pyridylmethyl)oxy]calix[4]arene. All the products were characterized by infrared spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction, and powder X-ray diffraction. Crystal structure analysis reveals that 1 holds a one-dimensional (1D) double-chain constructed by mononuclear [Cu(NO₃)] units and L linkers, while 2 features a 1D chain and its bowl-shaped L ligands work as linkers to connect the dinuclear [Cu₂Cl₄] units. Compounds 3 and 4 bear similar two-dimensional networks, in which each trinuclear [Cu₃Br₃]/[Cu₃I₃] unit works as a three-connecting node to connect its six equivalents by sharing L ligands. These results demonstrate that different anions have a significant effect on the final structure formation. Compounds 1?4 were employed as catalysts for the A³ coupling reaction under microwave irradiation. Notably, 3 showed the best catalytic properties for the synthesis of versatile propargylamines (yield up to 94% in only 10 min) from the A³ reaction of formaldehyde with a variety of alkynes and amines.

Full text of DOI:10.1021/acs.cgd.7b00898

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Article
Construction of Four Copper Coordination Polymers
Derived from a Tetra-Pyridyl-Functionalized Calix[4]arene:
Synthesis, Structural Diversity and Catalytic Applications
in the A3 (Aldehyde, Alkyne and Amine) Coupling Reaction
Cai-Xia Yu, Fei-Long Hu, Meng-Yu Liu, Cai-Wen Zhang, Yun-He Lv, Shu-Kuan Mao, and Lei-Lei Liu
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00898 • Publication Date (Web): 30 Aug 2017
Downloaded from http://pubs.acs.org on August 31, 2017
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Construction of Four Copper Coordination Polymers Derived from a
TetraꢀPyridylꢀFunctionalized Calix[4]arene: Synthesis, Structural
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Diversity and Catalytic Applications in the A (Aldehyde, Alkyne and
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Amine) Coupling Reaction
†
‡
†
†
,†
†
CaiꢀXia Yu, FeiꢀLong Hu, MengꢀYu Liu, CaiꢀWen Zhang, YunꢀHe Lv,* ShuꢀKuan Mao and
,
†
LeiꢀLei Liu*
†
Henan Key Laboratory of New Optoelectronic Functional Materials, College of Chemistry and
Chemical Engineering, Anyang Normal University, Anyang 455000, Henan, P. R. China
‡
Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi University for
Nationalities, Nanning, 530006, P. R. China
RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required
according to the journal that you are submitting your paper to)
* To whom correspondence should be addressed. Fax & Tel: Int. code +86 372 2900040; eꢀmail:
liuleileimail@163.com (L. L. Liu)
†
Anyang Normal University
‡
Guangxi University for Nationalities
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2 3
ABSTRACT: Solvothermal reactions of CuX (X = NO , Cl, Br, I) with tetraꢀpyridylꢀfunctionalized
calix[4]arene at 130 °C afforded four novel coordination polymers, {[(CuNO ) L]ꢁMeOH} (1),
3
2
n
[
(Cu
Cl
2 4
)L]
n
(2),
[(Cu
3
Br
3
)L]
n
(3)
and
[(Cu
3
I
3
)L]
n
(4),
where
L
=
25,26,27,28ꢀtetra[(3ꢀpyridylmethyl)oxy]calix[4]arene. All the products were characterized by infrared
spectroscopy, thermogravimetric analysis, singleꢀcrystal Xꢀray diffraction and powder Xꢀray
diffraction. Crystal structure analysis reveals that 1 holds a oneꢀdimensional (1D) doubleꢀchain
0
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0
constructed by mononuclear [Cu(NO
bowlꢀshaped L ligands work as linkers to connect the dinuclear [Cu
bear similar 2D networks, in which each trinuclear [Cu Br ]/[Cu ] unit works as a threeꢀconnecting
3
)] units and L linkers, while 2 features a 1D chain and its
2 4
Cl ] units. Compounds 3 and 4
3
3
3 3
I
node to connect its six equivalents by sharing L ligands. These results demonstrated that different
anions have significant effect on the final structure formation. Compounds 1–4 were employed as
3
catalysts for the A coupling reaction under microwave irradiation. Notably, 3 showed the best
catalytic properties for the synthesis of versatile propargylamines (yield up to 94% in only 10 min)
3
from the A reaction of formaldehyde with a variety of alkynes and amines.
Introduction
Owing to the procedural simplicity and synthetic efficiency, oneꢀpot multicomponent reactions
1
(
MCRs) have aroused wide concern in the past decades, which provided a feasible synthetic strategy
to access complex structures using rather simple starting materials by a oneꢀpot method, and exhibited
2
high selectivity and atom economy. An increasing number of MCRs have been designed for the
3
ꢀ8
synthesis of versatile structures with high yield and simple operation. Among various MCRs,
considerable attention have been paid to the catalytic coupling reaction of aldehyde, amine and alkyne
3
(soꢀcalled A coupling), as the main product propargylamine is the key and versatile intermediate to
9
ꢀ13
prepare many biologically active nitrogenꢀcontaining compounds.
Therefore, it is important to
3
explore an efficient catalyst with simple procedure for A coupling reaction.
Over the past several decades, calix[4]areneꢀbased molecules have emerged as a class of molecular
14ꢀ20
hosts due to their bowlꢀshaped cavity and ability to interact with various guest molecules.
Recently,
the calix[4]arenes and their derivatives have also been utilized as potential molecular units to construct
coordination polymers because of the easy modification and functionalization both on the lower and
21ꢀ27
upper rims.
Moreover, the calix[4]arene core displays inherent advantageous features, such as
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preorganization, flexibility and bulkiness skeleton, as well as its widely tolerance of functional
groups and metals. As a consequence, by tethering particular transition metals on such structure, the
asꢀsynthesized coordination polymers would be potential catalysts. The calix[4]arene platform
provides peculiar arrangement for the binding/catalytic site in a complementary array to
recognize/transform a potential substrate, which would be favorable for the design of versatile
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catalysts.
Furthermore, owing to the presence of the wellꢀdefined cavity near the catalytic centre,
we envisioned that the calix[4]areneꢀbased coordination polymers could give high selectivity for the
33,34
catalytic reaction.
Nowadays, it is widely acknowledged that the microwave irradiation have great advantages over
traditional heating because of its shorter reaction time, higher product yield and lower energy
35ꢀ41
consumption.
Thus, our studies report the microwaveꢀassisted Cu(I/II)ꢀcalix[4]areneꢀbased
catalysis as an efficient catalytic platform for direct access to propargylamines. Based on the design,
3
the Cu(I/II) ion was chosen as active site to catalyze the A reaction due to its high catalytic
1
2,42ꢀ49
activity.
[(3ꢀpyridylmethyl)oxy]calix[4]arene (denoted as L) was employed to assemble with copper salts, as
its abundant aromatic rings would facilitate the substrates alkyne to approach the active site of Cu(I/II)
The ligand
tetraꢀpyridylꢀfunctionalized calix[4]arene,
25,26,27,28ꢀtetra
ꢀ
1
8,50,51
ion through π–π interactions between the substrates and the aromatic rings.
coordination polymers, {[(CuNO L]ꢁMeOH} (1), [(Cu Cl )L] (2), [(Cu Br )L]
4) were synthesized by the assembly of L with CuX (X = NO
Hence, four
(3) and [(Cu )L]
3
)
2
n
2
4
n
3
3
n
3
I
3
n
(
2
3
, Cl, Br, I), giving different structural
3
architectures. Their catalytic activities were assessed by the microwaveꢀassisted A coupling reaction.
Interestingly, compound 3 exhibited the best catalytic properties for the synthesis of diverse
3
propargylamines (yield up to 94% in only 10 min) from the A reaction.
Experimental section
3 2 n 3 2 2
Preparation of {[(CuNO ) L]ꢁMeOH} (1). A solution of Cu(NO ) ·3H O (14 mg, 0.06 mmol), L
ligand (12 mg, 0.015 mmol), and 4 mL of MeOH/DMF (1:1 V/V, DMF = N,Nꢀdimethylformamide)
was sealed in a 10 mL Pyrex glass tube and heated at 130 °C for 3 days. Subsequent cooling to ambient
ꢀ1
temperature (5 °C h ) afforded the colorless blocks of 1. Yield: 7 mg (44%, based on L). Anal. Calcd.
for C53
H
48
N
6
2
Cu O11: C, 59.38; H, 4.51; N, 7.84. Found: C, 59.71; H, 4.17; N, 7.99. IR (KBr disc):
3
065 (w), 2916 (w), 1456 (m), 1430 (s), 1342 (m), 1236 (m), 1186 (s), 1086 (s), 987 (s), 949 (m), 801
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ꢀ1
(
s), 762 (s), 712 (s), 649 (m), 568 (w), 550 (w), 518 (m) cm .
Preparation of [(CuCl )L ] (2). A solution of CuCl ·2H O (3.5 mg, 0.02 mmol), L ligand (8 mg,
2
0.5 n
2
2
0
.01 mmol) and EtOH (4 mL) was sealed in a 10 mL Pyrex glass tube and heated at 130 °C for 3 days.
ꢀ1
Subsequent cooling to ambient temperature (5 °C h ) afforded the red blocks of 2. Yield: 5 mg (47%,
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based on L). Anal. Calcd. for C H N Cl CuO : C, 59.04; H, 4.19; N, 5.30. Found: C, 59.44; H, 3.95;
26
22
2
2
2
N, 5.69. IR (KBr disc): 3061 (w), 3000 (w), 2910 (w), 1600 (m), 1455 (s), 1425 (m), 1365 (w), 1245
(
m), 1185 (s), 1113 (m), 1082 (s), 1041 (m), 986 (s), 944 (m), 842 (m), 818 (m), 794 (m), 752 (s), 692
ꢀ1
(
s), 656 (m), 638 (m), 590 (m), 511 (w) cm .
Preparation of [(Cu Br )L] (3). Compound 3 (colorless blocks) was synthesized using a same
method as that of 2, except utilizing CuBr (4.5 mg, 0.02 mmol) and MeOH/DMF (1:1 V/V) instead of
CuCl ·2H O and EtOH. Yield: 7 mg (57%, based on L). Anal. Calcd. for C52 Cu Br : C, 51.22;
3
3
n
2
2
2
H
44
N
4
3
3 4
O
H, 3.64; N, 4.60. Found: C, 50.95; H, 3.37; N, 4.73. IR (KBr disc): 3059 (w), 2906 (w), 1572 (w), 1471
(m), 1455 (s), 1426 (s), 1397 (m), 1370 (m), 1245 (s), 1190 (s), 1093 (m), 1050 (m), 980 (s), 944 (m),
ꢀ
1
865 (w), 798 (m), 758 (s), 698 (s), 643 (m), 621 (w), 566 (m), 511 (w) cm .
Preparation of [(Cu I )L] (4). A solution of CuI (6 mg, 0.02 mmol), L ligand (8 mg, 0.01 mmol)
3 3
n
2
and DMF (4 mL) was sealed in a 10 mL Pyrex glass tube and heated at 130 °C for 3 days. Gradual
ꢀ1
cooling at a rate of 5 °C h to ambient temperature afforded the colorless blocks of 4. Yield: 7 mg
51%, based on L). Anal. Calcd. for C52 Cu : C, 45.91; H, 3.26; N, 4.12. Found: C, 45.49; H,
.98; N, 3.79. IR (KBr disc): 3061 (w), 2905 (w), 1575 (w), 1473 (m), 1456 (s), 1425 (s), 1395 (m),
371 (m), 1317 (w), 1245 (s), 1191 (s), 1089 (m), 1052 (m), 980 (s), 944 (m), 866 (w), 800 (m), 758 (s),
(
H
44
N
4
3 3 4
I O
2
1
ꢀ1
698 (s), 644 (m), 620 (w), 565 (m), 511 (w) cm .
Catalytic studies. The reactions of alkyne (1.0 mmol), amine (1.2 mmol), HCHO (1.2 mmol),
catalyst (0.001 mmol) and MeCN (10 mL) were conducted in a closed vessel containing under
microwave power (80 W) at 100 °C. After that, the system was cooled to ambient temperature and the
MeCN was removed by evaporation in vacuum. By diluting with 8 mL H O, the residual mixture was
2
extracted with ethyl acetate (3 × 10.0 mL). The combined organic phases were treated to remove the
solvent and further purified by column chromatography using petroleum ether/ethyl acetate as the
1
13
eluent to give the corresponding products. These products were characterized by H NMR, C NMR
and HRMS.
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Results and discussion
Synthetic and spectral aspects. Reactions of L ligand with Cu(NO ) ·3H O and CuX (X = Br, I)
3
2
2
2
in different solvents (MeOH/DMF for 1, MeOH/DMF for 3 and DMF for 4) at 130 °C for 3 days
afforded colorless crystals of 1 (44% yield), 3 (57% yield) and 4 (51% yield), respectively.
Interestingly, for compounds 1, 3 and 4, Cu(II) were reduced to Cu(I), which may stem from the
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reduction of Cu(II) was mediated by the DMF decomposition products. Similarly, reactions of
CuCl ·2H O with L ligand in EtOH produced red crystals of 2 (47% yield). To verify the valence of
2
2
copper in these compounds, XPS investigations were carried out. In Figure S1b, the peak of Cu 2p3/2 at
53
ca. 932.1 eV in 1, 3 and 4 are attributed to Cu(I). Compared Cu 2p XPS spectrum of 1, 3 and 4 with
that of 2, the higher binding energy of Cu 2p3/2 peak at 934.3 eV in 2 is assigned to Cu(II),
accompanied by the characteristic Cu(II) shakeup satellite peaks (938−945 eV) at 942.9 and 940.7
54ꢀ56
eV.
Compounds 1–4 were stable towards oxygen and moisture. PXRD measurements were carried out
to check their phase purity (Figure S2). Singleꢀcrystal diffraction analysis further confirmed the
identities of 1–4 and the corresponding crystallographic information were summarized in Table 1.
(Table 1 here)
Crystal structures. Compound 1 crystallizes in the orthorhombic space group Ibca. Its asymmetric
unit contains half of [(CuNO
3
)
2
L] unit and one MeOH molecule. In Figure 1a, each Cu centre is
−
threeꢀcoordinated by one O atom of one NO
3
anion and two pyridyl N atoms from one L ligand. A
flattened cone conformation was formed in calix[4]arene core of 1 (Figure 1a). The mononuclear
[Cu(NO )] subunit works as a 2ꢀconnected node to interconnect the L ligands, resulting in a 1D
[(CuNO ) L] doubleꢀchain (Figure 1b).
3
3
2
n
(Figure 1 here)
Compound 2 crystallizes in the monoclinic space group P2/n. Its asymmetric unit includes half of
−
[
(Cu Cl )L] unit. Each Cu(II) atom is fiveꢀcoordinated by three Cl anions and two pyridyl N atoms
2
4
from one L ligand, producing a distorted [CuN
2 3
Cl ] pentagonal pyramid coordination geometry
(Figure 2a). Similar to that in 1, a flattened cone conformation was also formed in the calix[4]arene
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core of 2, and parallel or sharply inclined position was observed for the opposed phenyl rings (Figure
2
2
a). Two [CuCl] subunits are connected by two ꢀ ꢀCl anions to form a dinuclear [Cu Cl ] unit (Figure
2
2
4
2 4
b). The Cu1···Cu1A separations are 3.4847(10) Å. These [Cu Cl ] units are also employed as
2ꢀconnected nodes to link L ligands through the N atoms of pyridyl arms, producing a 1D [(Cu
2 4 n
Cl )L]
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chain (Figure 2c).
(Figure 2 here)
Both compounds 3 and 4 crystallize in the monoclinic space group Cc. Their asymmetric units
include one [(Cu Br )L] and [(Cu )L] unit, respectively. While the Cu atoms in 3 and 4 adopted
different coordination geometries. For 3, Cu1 and Cu2 atoms adopt the same coordination geometries,
which is coordinated by one pyridyl N atom from one L ligand and two ꢀ ꢀBr atoms to complete the
3
3
3 3
I
2
triangular geometries (Figure 3a). The Cu3 atom is tetrahedrally coordinated by two pyridyl N atoms
from Lligands and two ꢀ ꢀBr atoms (Figure 3a). For 4, each Cu center is bonded with ꢀ ꢀI or ꢀ ꢀI atoms
2
2
3
and pyridyl N atoms from L ligands, resulting in the distorted [CuI
3
N]/[CuI
2
N
2
] tetrahedral
coordination geometries (Figure 3b). A flattened cone conformation was also formed in the
calix[4]arene core of 3 and 4, and parallel or sharply inclined position was observed for the opposed
phenyl rings (Figures 3aꢀ3b). As shown in Figures 3cꢀ3d, the Cu1, Cu2 and Cu3 centers are
2 2 3 3 3
interconnected by three ꢀ ꢀBr atoms or one ꢀ ꢀI and two ꢀ ꢀI atoms to afford the trinuclear [Cu Br ]
and [Cu ] units, respectively. The Cu···Cu separations are in the range of 2.5604(12)–2.9101(12) Å
3 3
I
3 3 3 3
and 2.4166(8)–2.8415(9) Å for 3 and 4. Furthermore, each [Cu Br ] or [Cu I ] unit in 3 and 4 connects
its three equivalents by sharing L ligands to give 2D networks (Figure 3e and Figure S3).
(Figure 3 here)
Thermal behavior. To investigate the thermal stability, thermogravimetric (TG) measurements of
1
–4 were conducted (Figure S4). In 1, the first weight loss of 2.46 % (calculated 2.99 %) at the
temperature range of 35–240 °C is attributed to MeOH solvent molecules. After that, further heating
lead to gradual decomposition of the compound. For 2–4, TG analysis indicated that they are stable up
to 255 °C (2), 295 °C (3) and 305 °C (4), then they begin to decompose.
Catalytic applications. Copper(I)/(II) complexes are fascinating not only for their interesting
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structures,
but also for their catalytic application in many organic transformations.
In order to
assess the catalytic utility of copper compounds 1–4 and further determine the best reaction conditions
3
to afford propargylamines with excellent yields, a series of A coupling reactions have been performed
under microwave irradiation using formaldehyde, amine and alkyne in the presence of copper catalysts
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1–4.
Initially, to optimize the reaction conditions, ethynylbenzene, formaldehyde and morpholine were
o
chosen as the model substrates (Table 2). Various copper catalysts (0.001 equiv) were tested at 100 C
in MeCN under microwave irradiation (Table 2, entries 1ꢀ4), resulting in the desired products with the
yields of trace, 62%, 91% and 78%, respectively. To ascertain the role of the structural features in
catalysis, the ESIꢀMS spectra of 1–4 were recorded. As shown in Figure S5, the base peak at
+
1
640.0834 in the spectra of 1 is attributed to [CuL
2
] fragment, in which the catalytic sites Cu(I) are
buried in the packing arrangement formed by L ligands that adopt the up and down modes (Figure 1b),
making the alkyne molecules difficult to approach the catalytic sites Cu(I). While, for 2–4, the peaks of
+
+
2 3 2 3 2
the spectra at 1812.5001, 1138.8334 and 1232.9167 are attributed to [(Cu Cl )L ] (2), [(Cu Br )L] (3)
+
and [(Cu I )L] (4) fragments, respectively. In the above fragments, the catalytic sites of Cu(I/II) are
3 2
exposed, as the L ligands arranged as single layer with the bowlꢀshaped fashions (Figure 2c and
Figures S6ꢀS7), which may facilitate the alkyne molecules to approach the active site Cu(I/II) through
18
the π–π interactions between alkyne and pyridyl rings of L ligands. Furthermore, open active sites
were obtained for 2–4 by losing halogen anions to effectively interact with substrates alkyne. In
comparison with 3 and 4, the species of copper in 2 are Cu(II), which have a lower catalytic activity
6
5,66
than Cu(I) to interact with the ethynylbenzene.
The active site Cu(I) in 3 and 4 are
threeꢀcoordinated and fourꢀcoordinated by N atoms and Br/I anions, which suggested that the Cu(I) in
3
3 have more active sites to catalyze the A coupling reaction, giving higher catalytic performance for 3.
Hence, compound 3 was finally selected as the catalyst for the reaction, considering its excellent
yield for expected product (Table 2, entry 3). Our next studies focused on the effect of solvent in the
model reaction. Considerably low yields were observed when other solvents such as toluene, DCE,
EtOH, and EtOAc were used (Table 2, entries 5ꢀ8), which may be due to catalyst 3 was insoluble in
o
o
these solvents. Lowering the reaction temperature to 60 C or 30 C, resulted in relatively low yields of
9% or 26% (Table 2, entries 9ꢀ10). The amount of catalyst is also an important factor in catalytic
3
reaction. As can be seen in Table 2, by lowering the amount of catalyst, a lower yield was obtained
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(
Table 2, entry 11) and no reaction occurred when the amount of copper catalyst was reduced to zero
Table 2, entry 12). After sufficient screening, the optimal condition eventually emerged as
(
ethynylbenzene (1.0 mmol), formaldehyde (1.2 mmol), morpholine (1.2 mmol), and MeCN (10.0 mL)
at 100 °C under microwave irradiation (Table 2, entry 3).
0
1
2
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9
0
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9
0
3
Furthermore, control catalytic experiments of A coupling reaction were performed under the same
condition. When the CuBr and L were employed as catalysts, the corresponding yields were 75% and 0
(Table 2, entries 13ꢀ14), respectively. The higher yield obtained for 3 (91%) may originate from the
introduction of L into the catalytic system that altered the coordination environment of the Cu(I) ions
and the interaction between Cu(I) centers and L in 3, resulting in the improvement of the catalytic
67
activity of copper centers.
(Table 2 here)
3
After our successful efforts, we shifted our attention to the scope of A coupling reaction catalyzed
by compound 3, and Table 3 exhibited the summarized results. Surprisingly, the reaction of
morpholine with both electronꢀdonating and electronꢀwithdrawing groups of pꢀsubstituted
phenylacetylene afforded the desired products with high yields of 92% and 94% (5bꢀ5c). It is
noteworthy that the reactions with sterically hindered polycyclic aromatic alkynes, such as
9
ꢀethynylphenanthrene and 1ꢀethynylpyrene, also proceeded smoothly to give the expected products
5
d and 5e in high yields. In addition, other representative secondary amines, such as pyrrolidine and
Nꢀbenzylethanamine, were also found to be suitable for this transformation and gave good to excellent
yields (5fꢀ5i). These results indicated that both the electronic effect of substituents and steric effects on
the aromatic alkynes had limited influence on this copperꢀcatalyzed threeꢀcomponent coupling
reaction. Further to compare the catalyst dosage to the literature methods, it is worth pointing out that
good to excellent yields were still obtained in the present protocol within 10 min, involving only 0.1
1
2,42,68,69
mol % catalyst loading without any additives.
(Table 3 here)
7
0,71
A plausible mechanism was proposed based on the experimental results and previous literature.
As demonstrated in Scheme 1, the catalyst 3 initially reacts with terminal alkyne to activate the C–H
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bond and form a copper–acetylide A (m/z 995.1152; Figure S8). This is a very favourable step because
72,73
Cu metal is well known to give high alkynophilicity for terminal alkynes.
The copper–acetylide A
further reacts with B (m/z 100.0761; Figure S9), which is generated in situ from morpholine and
formaldehyde, affording a coordinatively saturated intermediate C. Finally, the newly generated
intermediate C dissociates to afford the expected product 5a and regenerates the catalyst. The only
theoretical byꢀproduct in the reaction is water.
10
11
12
13
14
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16
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23
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56
57
58
59
60
(Scheme 1 here)
Conclusions
In this paper, four coordination polymers 1–4 have been constructed under the solvothermal reactions
between CuX (X = NO , Cl, Br, I) and tetraꢀpyridylꢀfunctionalized calix[4]arene (L). These
2
3
compounds exhibit different architectures, such as 1D chain, doubleꢀchain and 2D networks, which
demonstrates that a change in the species of anions played a crucial role in the selfꢀassembly process.
3
These coordination polymers have been employed in the A coupling reaction under microwave
3
irradiation and 3 give the best performance, which could effectively catalyze the A reaction of
formaldehyde with various alkynes and amines, producing the corresponding propargylamines with
high yields in a short time (yields up to 94% in 10 min). Such good performance can be attributed to its
abundant pyridyl rings facilitating the substrates alkyne to approach the active site of Cu(I) through
π–π interactions between the substrates and the pyridyl rings. The above observations provide further
evidence that copperꢀbased coordination polymers catalysis as an efficient catalytic platform for direct
access to the important intermediates of propargylamines, by a sustainable and atom economical
approach from easily accessible starting materials under mild conditions. Further studies of the
construction and applications of these coordination polymers are in progress.
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI:
1
0.1021/ 10.1021/acs.cgd.7b00xxxx.
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Xꢀray data collection and structure determination, XPS spectra, PXRD patterns, TGA curves,
1
13
ESIꢀSI spectra, H NMR, C NMR and HRMS spectra and additional figures (PDF).
Accession Codes
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
CCDC 1542817ꢀ1542820 contains the supplementary crystallographic data for this paper. These data
can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
Corresponding Author
*
*
Eꢀmail: liuleileimail@163.com (L.ꢀL.L.).
Eꢀmail: lvyunhe0217@163.com (Y.ꢀH.L.).
ORCID
LeiꢀLei Liu: 0000ꢀ0002ꢀ3372ꢀ2953
Notes
The authors declare no competing financial interest.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21401006 and
2
1701035), the Program for Science and Technology Innovation Talents at the University of Henan
Province (16HASTIT006) and the Young Teachers Funded Projects of University of Henan Province
(2015GGJSꢀ002).
References
(
(
(
(
(
1) Zhu, J.; Bienaymé, H. Multicomponent Reactions. John Wiley & Sons: 2006.
2) Bienaymé, H.; Hulme, C.; Oddon, G.; Schmitt, P. Chem. Eur. J. 2000, 6, 3321–3329.
3) Dömling, A.; Wang, W.; Wang, K. Chem. Rev. 2012, 112, 3083–3135.
4) Ruijter, E.; Scheffelaar, R.; Orru, R. V. A. Angew. Chem. Int. Ed. 2011, 50, 6234–6246.
5) Syamala, M. Org. Prep. Proced. Int. 2009, 41, 1–68.
10
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1
2
3
4
5
6
7
8
9
(
(
(
6) Bonne, D.; Coquerel, Y.; Constantieux, T.; Rodriguez, J. TetrahedronꢁAsymmetry 2010, 21, 1085–1109.
7) Karimi, B.; Gholinejad, M.; Khorasani, M. Chem. Commun. 2012, 48, 8961–8963.
8) Sharma, A.; Mejía, D.; Regnaud, A.; Uhlig, N.; Li, C. J.; Maysinger, D.; Kakkar, A. ACS Macro Lett. 2014, 3,
1079–1083.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(9) Konishi, M.; Ohkuma, H.; Tsuno, T.; Oki, T.; VanDuyne, G. D.; Clardy, J. J. Am. Chem. Soc. 1990, 112,
3715–3716.
(
(
(
(
10) Dyker, G. Angew. Chem. Int. Ed. 1999, 38, 1698–1712.
11) Gao, J.; Song, Q. W.; He, L. N.; Yang, Z. Z.; Dou, X. Y. Chem. Commun. 2012, 48, 2024–2026.
12) Peshkov, V. A.; Pereshivko, O. P.; Van der Eycken, E. V. Chem. Soc. Rev. 2012, 41, 3790–3807.
13) Layek, K.; Chakravarti, R.; Lakshmi Kantam, M.; Maheswaran, H.; Vinu, A. Green Chem. 2011, 13,
2
878–2887.
14) Kobayashi, K.; Yamanaka, M. Chem. Soc. Rev. 2015, 44, 449–466.
(
(15) Lv, L. L.; Yang, J.; Zhang, H. M.; Liu, Y. Y.; Ma, J. F. Inorg. Chem. 2015, 54, 1744–1755.
(16) Bonaccorso, C.; Nicoletta, F.; Zito, V.; Arena, G.; Sciotto, D.; Sgarlata, C. Supramol. Chem. 2013, 25, 615–625.
(17) Liu, L. L.; Ren, Z. G.; Wan, L. M.; Ding, H. Y.; Lang, J. P. CrystEngComm 2011, 13, 5718–5723.
(18) Liu, L. L.; Chen, J.; Yu, C. X.; Lv, W. X.; Yu, H. Y.; Cui, X. Q.; Liu, L. Dalton Trans. 2017, 46, 178–185.
(19)McLellan, R.; Palacios, M. A.; Beavers, C. M.; Teat, S. J.; Piligkos, S.; Brechin, E. K.; Dalgarno, S. J. Chem. Eur.
J. 2015, 21, 2804–2812.
20) Zeng, X.; Weng, L.; Chen, L.; Leng, X.; Ju, H.; He, X.; Zhang, Z. Z. J. Chem. Soc., Perkin Trans. 2 2001,
45–549.
(
5
(21) Dalgarno, S. J.; Tucker, S. A.; Bassil, D. B.; Atwood, J. L. Science 2005, 309, 2037–2039.
(22) Pasquale, S.; Sattin, S.; EscuderoꢀAdán, E. C.; MartínezꢀBelmonte, M.; de Mendoza, J. Nat. Commun. 2012, 3,
785–791.
(23) Hang, X.; Liu, B.; Zhu, X.; Wang, S.; Han, H.; Liao, W.; Liu, Y.; Hu, C. J. Am. Chem. Soc. 2016, 138,
2969–2972.
(
(
(
24) Liu, L. L.; Ren, Z. G.; Zhu, L. W.; Wang, H. F.; Yan, W. Y.; Lang, J. P. Cryst. Growth Des. 2011, 11, 3479–3488.
25) Shi, Q.; Luo, W. Z.; Li, B.; Xie, Y. P.; Zhang, T. Cryst. Growth Des. 2016, 16, 493–498.
26) Ovsyannikov, A.; Lang, M. N.; Ferlay, S.; Solovieva, S. E.; Antipin, I. S.; Konovalov, A. I.; Kyritsakas, N.;
Hosseini, M. W. Dalton Trans. 2013, 42, 116–126.
(27) Gao, J.; Ren, Z. G.; Lang, J. P. Chinese Chem. Lett. 2017, 28, 1087–1092.
11
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Page 12 of 23
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(
28) Casnati, A.; Pochini, A.; Ungaro, R.; Ugozzoli, F.; Arnaud, F.; Fanni, S.; Schwing, M. J.; Egberink, R. J.; Jong,
F.; Reinhoudt, D. N. J. Am. Chem. Soc. 1995, 117, 2767–2777.
29) Cobley, C. J.; Ellis, D. D.; Orpen, A. G.; Pringle, P. G. Dalton Trans. 2000, 1109–1112.
(
(30) Sémeril, D.; Jeunesse, C.; Matt, D.; Toupet, L. Angew. Chem. Int. Ed. 2006, 45, 5810–5814.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(31) Wan, L. M.; Li, H. X.; Zhao, W.; Ding, H. Y.; Fang, Y. Y.; Ni, P. H.; Lang, J. P. J. Polym. Sci. Part A: Pol. Chem.
2
012, 50, 4864–4870.
(32) Gao, J.; Ren, Z. G.; Lang, J. P. J. Organomet. Chem. 2015, 792, 88–92.
(33) Bonaccorso, C.; Brancatelli, G.; Ballistreri, F. P.; Geremia, S.; Pappalardo, A.; Tomaselli, G. A.; Toscano, R. M.;
Sciotto, D. Dalton Trans. 2014, 43, 2183–2193.
(
(
(
34) Nandi, P.; Solovyov, A.; Okrut, A.; Katz, A. ACS Catal. 2014, 4, 2492–2495.
35) Lidström, P.; Tierney, J.; Wathey, B.; Westman, J. Tetrahedron 2001, 57, 9225–9283.
36) Bagley, M. C.; Lubinu, M. C. In MicrowaveꢁAssisted Synthesis of Heterocycles; Springer: 2006, 31–58.
(37) Tanaka, K.; Kaupp, G. SolventꢁFree Organic Synthesis. John Wiley & Sons: 2009.
(38) de la Hoz, A.; Loupy, A. Microwaves in Organic Synthesis, 2 Volume Set. John Wiley & Sons: 2013.
(
(
(
(
(
(
39) Bariwal, J. B.; Ermolat'ev, D. S.; Van der Eycken, E. V. Chem. Eur. J. 2010, 16, 3281–3284.
40) Lang, J. P.; Tatsumi, K.; Kawaguchi, H.; Lu, J.; Ge, P.; Ji, W.; Shi, S. Inorg. Chem. 1996, 35, 7924–7927.
41) Hu, F. L.; Wang, H. F.; Guo, D.; Zhang, H.; Lang, J. P.; Beves, J. E. Chem. Commun. 2016, 52, 7990–7993.
42) Sagadevan, A.; Ragupathi, A.; Hwang, K. C. Angew. Chem. Int. Ed. 2015, 54, 13896–13901.
43) Zhao, H.; He, W.; Wei, L.; Cai, M. Catal. Sci. Technol. 2016, 6, 1488–1495.
44) Kidwai, M.; Bansal, V.; Mishra, N. K.; Kumar, A.; Mozumdar, S. Synlett. 2007, 10, 1581–1584.
(45) Feng, H.; Ermolat’ev, D. S.; Song, G.; Van der Eycken, E. V. J. Org. Chem. 2011, 76, 7608–7613.
(46) Tan, D. W.; Li, H. X.; Zhang, M. J.; Yao, J. L.; Lang, J. P. ChemCatChem 2017, 9, 1113–1118.
(47) Guo, B.; Xue, J. Y.; Li, H. X.; Tan, D. W.; Lang, J. P. RSC Adv. 2016, 6, 51687–51693.
(48) Wei, Z. H.; Ni, C. Y.; Li, H. X.; Ren, Z. G.; Sun, Z. R.; Lang, J. P. Chem. Commun. 2013, 49, 4836–4838.
(49) Wang, L.; Guo, B.; Li, H. X.; Li, Q.; Li, H. Y.; Lang, J. P. Dalton Trans. 2013, 42, 15570–15580.
(50) Fan, C. B.; Liu, Z. Q.; Gong, L. L.; Zheng, A. M.; Zhang, L.; Yan, C. S.; Wu, H. Q.; Feng, X. F.; Luo, F. Chem.
Commun. 2017, 53, 763–766.
51) Gong, L. L.; Yao, W. T.; Liu, Z. Q.; Zheng, A. M.; Li, J. Q.; Feng, X. F.; Ma, L. F.; Yan, C. S.; Luo, M. B.; Luo,
(
F. J. Mater. Chem. A 2017, 5, 7961–7967.
(52) Ding, S.; Jiao, N. Angew. Chem. Int. Ed. 2012, 51, 9226–9237.
12
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1
2
3
4
5
6
7
8
9
(
53) Bhide, V. G.; Salkalachen, S.; Rastog, A. C.; Rao, C. N. R.; Hegde, M. S. J. Phy. D: Appl. Phys. 1981, 14,
1
647–1656.
54) Liu, P.; Hensen, E. J. J. Am. Chem. Soc. 2013, 135, 14032–14035.
(
(55) Severino, F.; Brito, J. L.; Laine, J.; Fierro, J. L. G.; Agudo, A. L. J. Catal. 1998, 177, 82–95.
(56) Poulston, S.; Parlett, P.; Stone, P.; Bowker, M. Surf. Interface Anal. 1996, 24, 811–820.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(
57) Yu, J. H.; Xu, J. Q.; Ye, L.; Ding, H.; Xu, J. N.; Jia, H. B.; Wang, T. G.; Mu, Z. C.; Yang, G. D. J. Clust. Sci. 2003,
4, 1–8.
58) Yu, J. H.; Shi, Z.; Xu, J.; Chu, D.; Jin, W.; Ding, H.; Hua, J.; Xu, J.; Cui, X.; Wang, T. Pol. J. Chem. 2001, 75,
785–1789.
59) Huang, C.; Wu, J.; Song, C.; Ding, R.; Qiao, Y.; Hou, H.; Chang, J.; Fan, Y. Chem. Commun. 2015, 51,
0353–10356.
60) Ananthnag, G. S.; Mague, J. T.; Balakrishna, M. S. Inorg. Chem. 2015, 54, 10985–10992.
1
(
1
(
1
(
(61) Li, P. Z.; Wang, X. J.; Liu, J.; Lim, J. S.; Zou, R.; Zhao, Y. J. Am. Chem. Soc. 2016, 138, 2142–2145.
(62) Li, H. X.; Zhao, W.; Li, H. Y.; Xu, Z. L.; Wang, W. X.; Lang, J. P. Chem. Commun. 2013, 49, 4259–4261.
(
(
(
(
(
(
63) Zhang, M. J.; Li, H. X.; Li, H. Y.; Lang, J. P. Dalton Trans. 2016, 45, 17759–17769.
64) Choubey, B.; Radhakrishna, L.; Mague, J. T.; Balakrishna, M. S. Inorg. Chem. 2016, 55, 8514–8526.
65) Hein, J. E.; Fokin, V. V. Chem. Soc. Rev. 2010, 39, 1302–1315.
66) Chan, T. R.; Hilgraf, R.; Sharpless, K. B.; Fokin, V. V. Org. Lett. 2004, 6, 2853–2855.
67) Xi, Y.; Wei, W.; Xu, Y.; Huang, X.; Zhang, F.; Hu, C. W. Cryst. Growth Des. 2015, 15, 2695–2702.
68) Prakash, O.; Joshi, H.; Kumar, U.; Sharma, A. K.; Singh, A. K. Dalton Trans. 2015, 44, 1962–1968.
(69) Zhao, Y.; Song, Q. Org. Chem. Front. 2016, 3, 294–297.
(70) Feng, H.; Ermolat’ev, D. S.; Song, G.; Van der Eycken, E. V. Org. Lett. 2012, 14, 1942–1945.
(71) Borah, B. J.; Borah, S. J.; Saikia, L.; Dutta, D. K. Catal. Sci. Technol. 2014, 4, 1047–1054.
(
72) Borah, B. J.; Dutta, D.; Saikia, P. P.; Barua, N. C.; Dutta, D. K. Green Chem. 2011, 13, 3453–3460.
73) Albaladejo, M. J.; Alonso, F.; Moglie, Y.; Yus, M. Eur. J. Org. Chem. 2012, 3093–3104.
(
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Table 1. Summary of Crystallographic Data for 1−4
___________________________________________________________________________________________
Compound
____________________________________________________________________________________________
_
1
2
3
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
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2
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5
6
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9
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0
Empirical Formula
Formula Weight
Crystal System
Space Group
a (Å)
C
53
H
48Cu
2
N
6
O
11
C
26
H
22Cl
2
CuN
2
O
2
C
52
H
44Br
3
3
Cu N
4
O
4
52 3 3 4 4
C H44Cu I N O
1072.07
528.91
1219.27
1360.27
orthorhombic
Ibca
monoclinic
P2/n
monoclinic
Cc
monoclinic
Cc
15.196(3)
15.650(3)
39.540(8)
90
10.289(2)
16.890(3)
13.191(3)
90
24.543(5)
14.009(3)
16.521(3)
90
24.519(5)
14.249(3)
16.820(3)
90
b (Å)
c (Å)
α (°)
β (°)
90
95.83(3)
90
125.68(3)
90
125.76(3)
90
γ (°)
90
3
V (Å )
9403(3)
8
2280.5(8)
4
4614(2)
4
4769(2)
4
Z
T (K)
100
100
100
100
3
ρcalc (g/cm )
1.526
4448
1.541
1.755
1.895
F (000)
1084
2432
2648
ꢀ
1
µ
(MoKα, mm )
0.977
72387
1.220
4.020
3.318
Total reflections
19852
4031 (0.0720)
2987
15849
16375
Unique reflections (Rint) 4134 (0.0471)
7904 (0.0263)
7310
7311 (0.0208)
7158
No. of observations
3241
No. of parameters
349
299
615
595
a
R
1
0.0423
0.1274
1.050
0.0469
0.1284
1.031
0.0338
0.0769
1.041
0.0204
0.0476
1.031
b
wR
2
c
GOF
a
b
2
o
2 2
c
2 2 1/2
c
2
o
2 2
1/2
R = Σ||F |ꢀ|F |/Σ|F |. wR = {Σw(F ꢀF ) /Σw(F ) } . GOF = {Σw(F ꢀF ) /(nꢁp)} , where n = number of
1
o
c
o
2
o
c
reflections and p = total numbers of parameters refined.
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Table 2. Optimization of the reaction conditions
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_
___________________________________________________________________________________________
o
b
Entry
Catalyst
Solvent
T ( C)
Yield (%)
____________________________________________________________________________________________
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2
3
4
5
6
7
8
9
10
1
MeCN
MeCN
MeCN
MeCN
toluene
DCE
100
100
100
100
100
100
100
100
60
trace
62
91
78
16
54
15
49
39
26
32
0
2
3
4
3
3
3
EtOH
3
EtOAc
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
3
3
30
c
11
3
100
100
100
100
1
1
1
2
−
3
4
CuBr
L
75
0
____________________________________________________________________________________________
a
Reaction conditions: ethynylbenzene (1.0 mmol), formaldehyde (1.2 mmol), morpholine (1.2 mmol), Catalyst
b
c
(0.001 mmol), Solvent (10.0 mL), microwaves, 10 min. Yield of the isolated product. Catalyst (0.0005 mmol).
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3
a,b,c
Table 3. The scope of A coupling reaction catalyzed by 3
0
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9
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_
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_
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a
Standard reaction conditions: alkyne (1.0 mmol), formaldehyde (1.2 mmol), amine (1.2 mmol), 3 (0.001 mmol),
o
b
c
MeCN (10.0 mL), microwaves, 100 C, 10 min. Yield of the isolated products. The products of corresponding
1
13
propargylamines were characterized by H NMR, C NMR and HRMS (Figures S11ꢀS19).
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Captions for Schemes & Figures
3
Scheme 1. Plausible mechanism for the A coupling reaction catalyzed by compound 3.
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Figure 1. (a) View of the coordination environment of Cu centers in 1 with labeling schemes. Symmetry codes: (A) –
x + 1, – y + 1/2, z; (B) x – 1/2, – y + 1/2, – z + 2; (C) – x + 3/2, y, – z + 2. (b) View of a 1D [(CuNO
3 2 n
) L] chain of
1
. Atom color codes: Cu, cyan; O, red; N, blue; C, gray. All H atoms are omitted for clarity. Selected bond lengths (Å):
Cu(1)–N(1) 1.925(2), Cu(1)–N(2B) 1.929(2), Cu(1)–O(3) 2.256(5).
Figure 2. (a) View of the coordination environment of Cu center in 2 with labeling schemes. Symmetry codes: (A) –
x + 3/2, y, − z + 1/2; (B) x, y, z + 1; (C) – x + 3/2, y, − z − 1/2. (b) View of a [Cu Cl ] unit of 2. (c) View of a 1D
2
4
2 4 n
[(Cu Cl )L] chain in 2 extending along the c axis. Atom color codes: Cu, cyan; O, red; N, blue; C, gray; Cl, green.
All H atoms are omitted for clarity. Selected bond lengths (Å): Cu(1)–N(1) 1.993(3), Cu(1)–N(2B) 2.189(3),
Cu(1)–Cl(3) 2.2597(12), Cu(1)–Cl(2) 2.3236(11), Cu(1)–Cl(1) 2.3834(12).
Figure 3. (a) View of the coordination environment of Cu centers in 3 with labeling schemes. Symmetry codes: (A) x,
y – 1, z; (B) x, – y, z + 1/2. (b) View of the coordination environment of Cu centers in 4 with labeling schemes.
Symmetry codes: (A) x, y + 1, z; (B) x, – y + 2, z + 1/2. (c) View of a [CuBr] unit of 3. (d) View of a [CuI] unit of 4.
3
3
(
e) View of a 2D network in 3 extending along the bc plane. Atom color codes: Cu, cyan; O, red; N, blue; C, gray; Br,
dark yellow; I, pink. All H atoms are omitted for clarity. Selected bond lengths (Å) for 3: Cu(1)–N(1) 1.943(4),
Cu(1)–Br(3) 2.3986(15), Cu(1)–Br(1) 2.5036(11), Cu(2)–N(3A) 2.018(5), Cu(2)–Br(2) 2.3314(11), Cu(2)–Br(1)
2.3895(11), Cu(3)–N(2) 2.029(4), Cu(3)–N(4B) 2.040(4), Cu(3)–Br(3) 2.4859(9), Cu(3)–Br(2) 2.5365(15),
Cu(1)–Cu(2) 2.5901(12), Cu(1)–Cu(3) 2.9101(12), Cu(2)–Cu(3) 2.5604(12). Selected bond lengths (Å) for 4:
Cu(1)–N(2) 1.968(3), Cu(1)–I(3) 2.6268(8), Cu(1)–I(1) 2.7392(15), Cu(1)–I(2) 2.9571(9), Cu(2)–N(4A) 1.972(3),
Cu(2)–I(3) 2.6064(8), Cu(2)–I(2) 2.7247(9), Cu(2)–I(1) 2.8259(12), Cu(3)–N(1) 2.031(3), Cu(3)–N(3B) 2.041(3),
Cu(3)–I(1) 2.6416(7), Cu(3)–I(2) 2.6543(15), Cu(1)–Cu(2) 2.4166(8), Cu(1)–Cu(3) 2.8415(9), Cu(2)–Cu(3)
2
.5836(8).
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Scheme 1
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Figure 1
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(b)
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Figure 2
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Figure 3
(a)
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For Table of Contents Use Only
Short Text for TOC
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2 3
Solvothermal reactions of CuX (X = NO , Cl, Br, I) with tetraꢀpyridylꢀfunctionalized calix[4]arene
afforded four novel coordination polymers. Complexes 1ꢀ4 are characterized by infrared spectroscopy,
thermogravimetric analysis, singleꢀcrystal Xꢀray diffraction and powder Xꢀray diffraction. Complex 3
3
showed the best catalytic properties for the synthesis of versatile propargylamines from the A reaction
of formaldehyde with a variety of alkynes and amines.
Figure for TOC
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