Synthesis of click-chelator via Cu(I)-catalyzed alkyne-azide cycloaddition

Article abstract of DOI:10.1002/cjoc.201090368

The click-ligands based on 1,2,3-triazole and pyridine unit has been synthesized via Cu(I)-catalyzed alkyne-azide cycloaddition from corresponding organic azides and terminal alkynes. The ligand structure was characterized by NMR, IR and elemental analysis as well as single crystal diffractions. The single crystal structure of the complexes from two different ligands coordinating to Cu(II) and Co(II) ions indicated that the N(2) atom in 1,2,3-triazole unit can act as an efficient donor to metals through the rational molecular design. Copyright

Full text of DOI:10.1002/cjoc.201090368

FULL PAPER
Synthesis of Click-Chelator via Cu(I)-Catalyzed Alkyne-Azide
Cycloaddition
Fu, Yanga(傅杨)
Liu, Yana(刘炎)
Fu, Xiaopinga(付晓平)
Zou, Lia(邹丽)
Li, Huaa(李桦)
Li, Mingb(李明)
Chen, Xingguo*,a(陈兴国)
Qin, Jinguia(秦金贵)
aDepartment of Chemistry and Hubei Key Laboratory on Organic and Polymeric Opto-Electronic Materials,
Wuhan University, Wuhan, Hubei 430072, China
b College of Chemical Engineering, Wuhan Textile University, Wuhan, Hubei 430074, China
The click-ligands based on 1,2,3-triazole and pyridine unit has been synthesized via Cu(I)-catalyzed alkyne-
azide cycloaddition from corresponding organic azides and terminal alkynes. The ligand structure was characterized
by NMR, IR and elemental analysis as well as single crystal diffractions. The single crystal structure of the com-
plexes from two different ligands coordinating to Cu(II) and Co(II) ions indicated that the N(2) atom in
1,2,3-triazole unit can act as an efficient donor to metals through the rational molecular design.
Keywords Click Chemistry, ligand design, N ligands, synthesis
Introduction
In addition, the theoretical calculation revealed that
N(2) atom in 1,2,3-triazole has much lower electron
density than N(3), indicating that N(2) atom is not a
good coordinating site compared to N(3), which was
also supported by some experimental results.10-13 Since
N(2) atom has an electron pair as well, it can also coor-
dinate to metal via rational molecular design. Thus,
synthesis of new 1,2,3-triazole-based ligands and study
on the coordinate ability of N(2) atom in 1,2,3-triazole
deserve to be further attempted, which will expand the
coordination chemistry or supramolecular chemistry of
1,2,3-triazole-based ligands. So we synthesized a series
of click-ligands based on 1,2,3-triazole and pyridine
group via CuAAC reaction and also obtained several
Cu(II) or Co(II) metal complexes from two simple
Since the birth of coordination chemistry in 1896,
searching for new kind of ligands has drawn a continu-
ous attention. Especially, the multi-dentate chelating
ligand as the building block plays a crucial role in con-
structing different types of supramolecular structure and
can also be used to prepare variety kinds of functional
materials.1 However, design of new ligand is still some-
times a challenge to the chemist due to the multi-step
synthesis and rigorous synthetic conditions. Recently,
the “Click Reaction” firstly introduced by Sharpless and
co-workers affords a good way to achieve this target.2
Among them, the Cu(I)-catalyzed alkyne-azide [3＋2]
cycloaddition (CuAAC reaction) is a typical one to
synthesize the 1,4-disubsituted-1,2,3-triazoles. Due to
its much mild reaction conditions, well-easily experi-
mental manipulation, high efficiency and excellent re-
gio-selectivity,3 it has been widely used in many areas
such as molecular biology, supramolecular assembly,
new medicine design, nano-optoelectronics and materi-
als science.4 In these applications 1,2,3-triazole only
acts as a simple linkage. As a stable aromatic heterocy-
cle, the 1,2,3-triazole also contains two nitrogen atoms
[N(2) and N(3)] with one pair of non-covalent electrons,
indicating both of them can act as donors to coordinate
with different metals.3 Recent research revealed that
N(3) atom of 1,2,3-triazole unit did take part in the co-
ordination with metal,4,5 which was confirmed by single
crystal analysis. So 1,2,3-triazole-based ligands from
CuAAC reaction have been applied in catalyst, ra-
dio-active labeling medicines, organometallics,5-12 etc.
ligands,
2-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]
pyridine (3a) and 4-[(4-phenyl-1H-1,2,3-triazol-1-yl)-
methyl] pyridine (3c). The crystal data indicated that the
N(2) atom of 1,2,3-triazole can efficiently participate in
the coordination to metals through the molecular design
of “chelate effect”.1
Results and discussion
Synthesis
The synthetic routes for the click-ligands are shown in
Schemes 1—3. All the azides used in CuAAC reaction
were synthesized via the classical SN2 reaction from 2, 3,
or 4-(chloromethyl)pyridine with sodium azide in ace-
tonitrile.14 The alkynes were prepared through Pd(0)-
catalyzed Sonogashira coupling from the corresponding
bromo- or iodine-aromatic compounds and ethynyl-
*
E-mail: xgchen@whu.edu.cn
Received February 12, 2010; revised May 27, 2010; accepted June 2, 2010.
Project supported by the National Natural Science Foundation of China (No. 20774071).
2226
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 2226— 2232

Synthesis of Click-Chelator via Cu (I)-Catalyzed Alkyne-Azide Cycloaddition
trimethylsilane.15 The CuAAC reaction was carried out
in a typical procedure described in reference,3 in which
in-situ generated Cu(I) cation had been employed as
catalyst and excess azides was applied to ensure the full
conversion of alkyne component. In each reaction, 2%
molar ratio of the catalyst and 10% molar ratio of the
reducing reagent in aqueous solution (fresh-generated
sodium ascorbate) had been added. The excess ascorb-
ate can prevent the oxidation of Cu(I) to Cu(II) ion.3
The starting materials including mono-, bis- or tri-al-
kynes was employed to prepare different multi-dentate
chelate ligands. It was found that compounds 4a—4c
can precipitate from the reaction system during the re-
action due to their low solubility in common solvents.
Thus, considering solubility of the different products as
well as starting compounds, THF was utilized instead of
t-BuOH in the synthesis of compounds 5a—8.
results with metals.
Crystal sructures16
The substituted group at N(1) atom of 1,2,3-triazole
in 3a is 2-methylpyridine, which can co-coordinate to
metal with nitrogen atom of pyridine (Npy) to form a
six-membered chelate ring. However, in 3b and 3c the
substituted group is 3-methylpyridine and 4-methyl-
pyridine respectively, so both of them can hardly form
stable chelating ring with metal. In order to investigate
the coordinating ability of N(2) atom in different kinds
of liagnds, we selected 3a—3c to react with CuCl2 at
same reaction condition. Two complexes, Cu(II)-3a17
and Cu(II)-3c, had been obtained and their crystal
structures were determined as in Figures 1 and 2, re-
spectively. The corresponding complex of 3b was not
obtained, although it had been tried for several times
with different synthetic routes.
As expected, the N(2) atom did co-coordinate to the
metals with Npy atom to form the stable six-membered
chelate ring in Cu(II)-3a. While in Cu(II)-3c only Npy
atom coordinated to Cu(II) ion, in which N(2) and N(3)
of 1,2,3-triazole unit did not participate the coordination.
In Cu(II)-3a, Cu(II) is in a distorted octahedral geome-
try, in which the bond distance between Cu(II) and Npy
is 2.040 Å and the bond distance of N(2) and Cu(II) is
Generally, the reaction mixture had been kept stir-
ring smoothly under 50 ℃ for 12 h to make sure that
all alkynes were converted to products. They were puri-
fied by chromatography with different eluent and ob-
tained in high yields (except for compounds 4a—4c, the
relatively low yields are due to poor solubility in com-
mon organic solvents). So the long-chain alkyl group
was introduced into the click-chelators to improve the
solubility, which can possibly affect the final assembly
Scheme 1 Synthetic routes for 3a—3c and 4a—4c
N
Ar
N3
1a - 1c
+
+
H
Ar
N
N
2a
2b
(i), (ii), (iii)
3a - 3c
N
Ar
N
N
N
N
2
Ar
H
H
N3
Ar
N
N
1a - 1c
4a - 4c
N
Ar =
N
1a, 3a, 4a
1b, 3b, 4b
1c, 3c, 4c
(i) 2 mol% CuSO4•5H2O, 10 mol% NaHCO3,10 mol% ascorbic acid; (ii) t-BuOH/H2O (V/V＝1/1); (iii) 50 ℃, 12 h.
Scheme 2 Synthetic route for 5a—7b
N
N
(i), (ii), (iii)
N
H
Ar
H
+ 2
Ar
N
N
N
N
N
2c - 2h
N3
1a
5a - 7b
OR
Ar =
RO
N
R
R
R
R = hexyl
R = dodecyl
2c, 5a
2d, 5b
2e, 6a
2f, 6b
2g, 7a
2h, 7b
(i) 2 mol% CuSO4•5H2O, 10 mol% NaHCO3,10 mol% ascorbic acid; (ii) THF/H2O (V/V＝2/1); (iii) 50 ℃, 12 h.
Chin. J. Chem. 2010, 28, 2226— 2232
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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Fu et al.
FULL PAPER
Scheme 3 Synthetic route for 8
Table 1 Reactants and separation condition for the click-ligands
H
No. Azide
Alkyne
Eluent
Yield%
80
Ethyl acetate/Petroleum
(V/V＝2/1)
3a
1a
2a
3b
3c
4a
4b
4c
1b
1c
1a
1b
1c
2a
2a
2b
2b
2b
Ethyl acetate
85
88
51a
49a
50a
(i), (ii), (iii)
3
+
Ethyl acetate
N
DCM/Methanol (V/V＝18/1)
DCM/Methanol (V/V＝18/1)
DCM/Methanol (V/V＝10/1)
N3
N
1a
H
H
5a
1a
2c
DCM/Methanol (V/V＝18/1)
70
5b
6a
1a
1a
2d
2e
DCM/Methanol (V/V＝18/1)
94
81
DCM/Methanol (V/V＝18/1)
2i
6b
7a
1a
1a
2f
DCM/Methanol (V/V＝18/1)
DCM/Methanol (V/V＝18/1)
93
94
2g
N
7b
1a
2h
DCM/Methanol (V/V＝18/1)
92
8
1a
2i
DCM/Methanol (V/V＝18/1)
90
N N
a The low yields of 4a—4c were due to their poor solubility in the
N
solvent used as eluent.
In order to further study the coordinating ability of
N(2) atom with different metals, another complex of
Co(II)-3a was obtained and its crystal structure is shown
in Figure 3. It showed similar coordination geometry to
Cu(II)-3a. The bond distance between Co(II) ion and
N(2) is 2.196 Å and the bond distance between Co(II)
and Npy is 2.185 Å. The difference between two Co—N
bonds is only 0.011 Å, indicating that N(2) atom exhib-
its comparable coordinating ability with Npy. From
above results of Cu(II)-3a and Co(II)-3a, it can be seen
that the coordinating ability of N(2) atom in 1,2,3-
triazole is different when it coordinates to different met-
als. Therefore, it can be concluded that the coordi-
N
N
N
N
N
N
N
N
N
8
(i) 2 mol% CuSO4•5H2O, 10 mol% NaHCO3,10 mol% ascorbic acid;; (ii)
THF/H2O (V/V＝2/1); (iii) 50 ℃, 12 h.
2.715 Å. The difference of 0.675 Å between two Cu(II)
—N bonds indicates that the coordinating ability of N(2)
atom is much weaker than that of Npy in Cu(II)-3a.
Figure 1 Crystal structure of Cu(II)-3a.
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Chin. J. Chem. 2010, 28, 2226—2232

Synthesis of Click-Chelator via Cu (I)-Catalyzed Alkyne-Azide Cycloaddition
Figure 2 Crystal structure of Cu(II)-3c (the water has been omitted for clarity).
Figure 3 Crystal structure of Co(II)-3a.
nating ability of N(2) atom of 1,2,3-triazole in different
7b and 8 based on the structure of 3a are designed and
synthesized. Their coordination with different metals is
in progress.
type of ligands such as 3a—3c is much different, and its
coordinating ability is also different when it coordinates
to different metals. And the N(2) atom can act as an
effective donor to metal via the rational molecular de-
sign such as “chelate effect”.
Conclusion
Via Cu(I)-catalyzed click reaction a series of ligands
based on 1,2,3-triazole unit have been designed and
synthesized. All these ligands can be easily prepared in
high yields and their structures have been characterized
by NMR, IR, MS and elemental analysis. Three com-
plexes from ligands 3a and 3c have been obtained and
the crystal structure was determined, which confirmed
that the N(2) atom in 1,2,3-triazole unit can act as an
effective donor to coordinate with metals via the ration-
al molecular design. The coordination behaviors of
these ligands are now under further investigation, which
may be applied in organic-inorganic hybrid opto-elec-
tronic materials in the future.
At same time, single crystal of 5a was obtained by
slow diffusion of methanol to its dichloromethane solu-
tion and its crystal structure was determined with X-ray
diffraction method as shown in Figure 4. It can be seen
that the N(2) atom of 1,2,3-triazole and Npy atom in
2-pyridine adopt a “U” shape conformation that will
form a stable six-membered chelate ring when they co-
ordinate with the metal ions. This supports the above
research results.
Obviously, the position of Npy atom in pyridine unit
greatly affects the coordinating ability of N(2) atom in
this kind of click-ligands. Thus, a series of new
multi-chelating click-ligands such as 5a, 5b, 6a, 6b, 7a,
Chin. J. Chem. 2010, 28, 2226—2232
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Fu et al.
FULL PAPER
Figure 4 Crystal structure of 5a.
Experimental
8.61 (d, J＝3.9 Hz, 1H), 7.94 (s, 1H), 7.83 (d, J＝7.5
Hz, 2H), 7.70 (t, J＝7.5 Hz, 1H), 7.41 (t, J＝7.5 Hz,
2H), 7.34—7.25 (m, 3H), 5.71 (s, 2H); 13C NMR
(CDCl3, 300 MHz) δ: 55.9, 120.5, 122.6, 123.7, 125.9,
128.4, 129.0, 130.7, 137.6, 148.4, 145.0, 154.7; IR (KBr)
ν: 3118, 3092, 3044, 3008, 2982, 2942, 2913, 1591,
1478, 1433, 1357, 1331, 1290, 1222, 1195, 1150, 1076,
1050, 1076, 1050, 994, 970, 912, 841, 816, 770, 749,
Reagents and instruments
1H NMR and 13C NMR spectra were recorded on a
Varian MECUYRVX300 spectrometer in CDCl3 using
tetramethylsilane (TMS) as an internal reference. Ele-
mental analyses of carbon, hydrogen, and nitrogen were
performed on a Carlorerba-1106 microanalyzer. FT-IR
experiment was carried out on a NICOLET 170SX
FT-IR spectrometer with KBr pellets. Mass spectrome-
try was performed on a Finnigan Trance Mass spec-
trometer. The determination of crystal structure was
performed on a Bruker Smart APEX II CCD detector
using graphite monochromated Mo Kα radiation (λ＝
0.71073 Å). All the chemicals and reagents employed in
the experiments were commercial available and used
without further purification.
－1
719, 695, 588, 560, 512, 475 cm ; MS (EI) m/z: 237.2
(M＋). Anal. calcd for C14H12N4: C 71.17, H 5.12, N
23.71; found C 71.55, H 4.81, N 23.33.
Compound 3b 1H NMR (CDCl3, 300 MHz) δ:
8.66 (s, 1H), 8.64 (d, J＝4.5 Hz, 1H), 7.80 (d, J＝7.2
Hz), 7.71 (s, 1H), 7.64 (d, J＝7.8 Hz, 1H), 7.41 (t, J＝
7.2 Hz, 2H), 7.31 (t, J＝6.9 Hz, 2H), 5.62 (s, 2H); 13C
NMR (CDCl3, 300 MHz) δ: 51.6, 119.4, 125.7, 128.4,
128.8, 130.2, 135.6, 148.6, 149.0, 150.2; IR (KBr) ν:
3128, 3094, 3058, 3030, 2985, 2948, 1597, 1576, 1481,
1463, 1425, 1355, 1336, 1223, 1189, 1136, 1074, 1048,
General methods for ligand synthesis
－1
The organic azides and all the bis-alkyls were syn-
thesized according to the published methods.13,14 The
ligands were synthesized according to Ref. 5 (different
solvent system was used for different starting materials
indicated in Schemes 1—3): the alkyne (1.0 equiv.) was
put into the flask with 30 mL of mixed solvent, then the
fresh generated sodium ascorbate aqueous solution (10
mol%, 5 mL) was added, followed by CuSO4•5H2O
aqueous solution (2 mol%, 5 mL). The organic azide
(1.1 equiv. for each alkyne group in each molecule) was
added finally. The mixture was stirred under 50 ℃ for
12 h, then cooled to room temperature, poured into 100
mL of ice cooled water. After 1 h, it was extracted with
CH2Cl2, and the organic layer was collected and dried
over MgSO4. After filtration, the concentrated crude
product was purified by chromotography (Table 1) and
further purified by recrystallization.
1031, 919, 814, 759, 700, 592, 560, 512 cm ; MS (EI)
m/z: 237.2 (M＋). Anal. calcd for C14H12N4: C 71.17, H
5.12, N 23.71; found C 71.28, H 5.30, N 24.07.
Compound 3c 1H NMR (CDCl3, 300 MHz) δ:
8.65 (s, 2H), 7.83 (d, J＝7.2 Hz, 2H), 7.76 (s, 1H), 7.43
(t, J＝6.9 Hz, 2H), 7.37 (t, J＝6.9 Hz, 1H), 7.18 (s, 2H),
5.63 (s, 2H); 13C NMR (CDCl3, 300 MHz) δ: 52.0,
119.4, 121.4, 125.0, 127.8, 128.2, 129.4, 143.0, 147.8,
149.8; IR (KBr) ν: 3116, 3089, 3032, 2944, 1602, 1561,
1483, 1464, 1438, 1417, 1350, 1224, 1189, 1077, 1047,
－1
973, 908, 859, 822, 765＋, 718, 692, 583, 508, 486 cm ;
MS (EI) m/z: 237.2 (M ). Anal. calcd for C14H12N4: C
71.17, H 5.12, N 23.71; found C 71.23, H 5.16, N 24.03.
Compound 4a 1H NMR (CDCl3, 300 MHz) δ:
8.59 (d, J＝3.9 Hz, 2H), 7.93 (s, 2H), 7.85 (s, 4H), 7.67
(t, J1＝7.5 Hz, J2＝8.1 Hz, 2H), 7.27—7.21 (m, 4H),
5.67 (s, 4H); 13C NMR (CDCl3, 300 MHz) δ: 55.3,
122.9, 124.0, 126.3, 130.8, 138.1, 146.9, 150.2, 155.6;
IR (KBr) ν: 3147, 3094, 3050, 3005, 2921, 2851, 1591,
1569, 1497, 1461, 1434, 1387, 1361, 1316, 1294, 1263,
1236, 1204, 1171, 1150, 1075, 1047, 1002, 938, 874,
Caution: The organic azides and sodium azide are
potentially explosive hazards, they should be stored in a
refrigerator and handled with great care!
Characterization data for all compounds
＋
－1
845, 797, 715, 598 cm ; MS (EI) m/z: 394.2 (M ).
Compound 3a 1H NMR (CDCl3, 300 MHz) δ:
Anal. calcd for C22H18N8: C 66.99, H 4.60, N 28.41;
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© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 2226—2232

Synthesis of Click-Chelator via Cu (I)-Catalyzed Alkyne-Azide Cycloaddition
found C 67.26, H 4.46, N 28.21.
Compound 4b 1H NMR (DMSO, 300 MHz) δ:
2H), 1.84—1.81 (m, 2H), 1.34—1.22 (m, 6H), 0.83 (t,
J＝5.1 Hz, 3H); 13C NMR (CDCl3, 400 MHz) δ: 13.9,
8.72 (s, 2H), 8.67 (s, 2H), 8.57 (d, J＝3.9 Hz, 2H), 7.92
(s, 4H), 7.78 (d, J＝7.8 Hz, 2H), 7.46—7.41 (m, 2H),
5.73 (s, 4H); IR (KBr) ν: 3128, 3095, 3013, 2951, 2928,
2859, 1639, 1598, 1575, 1479, 1453, 1433, 1358, 1316,
1256, 1220, 1150, 1075,－1047, 996, 975, 891, 832, 806,
22.4, 26.8, 28.8, 31.4, 43.1, 55.6, 117.8, 119.4, 121.6,
122.3, 123.0, 123.3, 123.8, 137.3, 140.6, 149.0, 149.7,
154.6; IR (KBr) ν: 3128, 3095, 3013, 2951, 2928, 2859,
1639, 1598, 1575, 1479, 1453, 1433, 1358, 1316, 1256,
1220, 1150, 1075,－1047, 996, 975, 891, 832, 806, 751,
＋
＋
1
1
751, 722, 601, 565 cm ; MS (EI) m/z: 394.8 (M ).
Anal. calcd for C22H18N8: C 66.99, H 4.60, N 28.41;
found C 67.24, H 4.11, N 28.68.
722, 601, 565 cm ; MS (EI) m/z: 567.7 (M ). Anal.
calcd for C34H33N9: C 71.93, H 5.86, N 22.21; found C
71.61, H 5.48, N 22.13.
Compound 4c 1H NMR (DMSO, 300 MHz) δ:
Compound 6b 1H NMR (CDCl3, 300 MHz) δ:
8.65 (d, J＝3.0 Hz, 4H), 7.90 (s, 4H), 7.79 (s, 2H), 7.17
Note: For compounds 4b and 4c, due to their low
solubility in DMSO-d6, it was unable to obtain clear
signals when trying to obtain the 13C NMR spectra of
these two samples. And the solubility of these three
compounds was very low for their rigid structure, for
the rich containing of nitrogen atoms, they might be
seriously attached to the silica, so the separation yield
8.66 (d, J＝4.5 Hz, 2H), 8.56 (s, 2H), 7.98 (t, J＝6.9 Hz,
(d, J＝5.1 Hz, 4H), 5.73 (s, 4H); IR (KBr) ν: 3129, 3077,
4H), 7.72 (t, J＝6.3 Hz, 2H), 7.44 (d, J＝8.4 Hz, 2H),
3021, 2927, 2853, 1592, 1460, 1435, 1363, 1306, 1227,
1193, 1143, 1075, 1047, 989, 900, 851, 827, 798, 753,
720, 605, 557, 452 cm ; MS (EI) m/z: 394.4 (M ).
Anal. calcd for C22H18N8: C 66.99, H 4.60, N 28.41;
found C 66.78, H 4.42, N 28.31.
7.31—7.26 (m, 4H), 5.75 (s, 4H), 4.31 (t, J＝6.9 Hz,
2H), 1.89 (m, 2H), 1.40—0.84 (m, 18H), 0.86 (t, J＝6.3
Hz, 6H); 13C NMR (CDCl3, 400 MHz) δ: 12.3, 22.8,
27.4, 29.1, 29.5, 29.7, 32.0, 43.4, 55.9, 109.3, 118.0,
119.6, 121.9, 122.6, 123.2, 123.6, 124.1, 137.5, 140.9,
149.3, 149.9, 154.8; IR (KBr) ν: 3139, 3094, 3055, 3013,
2923, 2851, 1648, 1631, 1614, 1593, 1479, 1438, 1354,
1318, 1252, 1220, 1148,－1078, 1049, 994, 887, 847, 8＋04,
＋
－1
1
757, 721, 563, 477 cm ; MS (EI) m/z: 651.9 (M ).
Anal. calcd for C40H45N9: C 73.70, H 6.96, N 19.34;
found C 74.15, H 7.06, N 19.56.
Compound 7a 1H NMR (CDCl3, 300 MHz) δ:
was relatively low.
8.64 (d, J＝5.2 Hz, 2H), 8.01 (s, 2H), 7.90 (s, 2H), 7.77
Compound 5a 1H NMR (CDCl3, 300 MHz) δ:
—7.69 (m, 6H), 7.31—7.27 (m, 4H), 5.73 (s, 4H), 2.06
8.62 (d, J＝4.5 Hz, 2H), 8.24 (s, 2H), 7.99 (s, 2H), 7.68
—2.01 (m, 4H), 1.22—0.96 (m, 12H), 0.71 (t, J＝6.9
(t, 2H), 7.29—7.25 (m, 2H), 7.16 (d J＝7.8 Hz, 2H),
Hz, 6H), 0.60 (m, 4H); 13C NMR (CDCl3, 400 MHz) δ:
5.73 (s, 4H), 4.15 (t, 4H), 1.87—1.78 (m, 4H), 1.43—
1.40 (m, 4H), 1.30—1.28 (m, 8H), 0.88 (t, J＝6.3 Hz,
6H); 13C NMR (CDCl3, 300 MHz) δ: 13.9, 22.5, 25.7,
29.3, 31.4, 55.5, 68.8, 110.5, 119.1, 122.01, 123.0,
123.2, 123.8, 137.2, 143.6, 149.3, 149.6, 154.8; IR (KBr)
ν: 3147, 3094, 3050, 3005, 2921, 2851, 1591, 1569,
1497, 1461, 1434, 1387, 1361, 1316, 1294, 1263, 1236,
1204, 1171, 1150, 1075, 1047, 1002, 938＋, 874, 845, 797,
14.2, 22.8, 24.0, 29.9, 31.8, 40.8, 55.7, 56.0, 119.97,
120.2, 120.3, 120.4, 122.6, 123.7, 124.8, 130.0, 137.7,
141.1, 149.0, 150.0, 152.0, 154.7; IR (KBr) ν: 3129,
3077, 3021, 2927, 2853, 1592, 1460, 1435, 1363, 1306,
1227, 1193, 1143, 1075, 1047, 989, 900, 851, 827, 798,
＋
－1
753, 720, 605, 557, 452 cm ; MS (EI) m/z: 650.9 (M ).
Anal. calcd for C41H46N8: C 75.66, H 7.12, N 17.22;
found C 75.81, H 6.79, N 17.53.
－1
715, 598 cm ; MS (EI) m/z: 594.8 (M ). Anal. calcd
Compound 7b 1H NMR (CDCl3, 300 MHz) δ:
for C34H42N8O2: C 68.66, H 7.12, N 18.84; found C
68.87, H 6.93, N 18.89.
Compound 5b 1H NMR (CDCl3, 300 MHz) δ:
8.62 (d, J＝6.0 Hz, 2H), 7.99 (s, 2H), 7.88 (s, 2H), 7.73
—7.68 (m, 6H), 7.29—7.25 (m, 4H), 5.72 (s, 4H), 2.03
—1.99 (m, 4H), 1.24—0.98 (m, 36H), 0.84 (t, J＝6.6
8.63 (d, J＝4.5 Hz, 2H), 8.26 (s, 2H), 7.99 (s, 2H), 7.71
Hz, 6H), 0.60 (m, 4H); 13C NMR (CDCl3, 300 MHz) δ:
14.3, 22.8, 27.4, 29.1, 29.5, 29.7, 32.0, 43.4, 55.9, 109.3,
118.0, 119.6, 121.9, 122.6, 123.2, 123.6, 124.1, 137.5,
140.1, 149.3, 149.9, 154.8; IR (KBr) ν: 3162, 3083,
3055, 3016, 2923, 2848, 1592, 1570, 1500, 1467, 1432,
1381, 1342, 1237,－1202, 1067, 1038, 1002, 880, 830,
(t, J＝7.5 Hz, 2H), 7.31—7.26 (m, 2H), 7.20 (d, J＝7.8
Hz), 5.76 (s, 4H), 4.15 (t, J＝6.6 Hz, 4H), 1.85—1.78
(m, 8H), 1.42—1.25 (m, 32H), 0.88 (t, 6H, m, the pro-
ton signal from alkyl chain, 46H); 13C NMR (CDCl3,
300 MHz) δ: 14.4, 22.9, 26.4, 29.6, 29.9, 32.1, 55.8,
69.1, 10.9, 119.4, 122.4, 123.5, 124.2, 137.5, 143.9,
149.7, 149.9, 155.2; IR (KBr) ν: 3162, 3083, 3055, 3016,
2923, 2848, 1592, 1569, 1500, 1467, 1432, 1381, 1342,
1381, 1342, 1237,－1202, 1067, 1038, 1002, 880, 830,
＋
1
756, 721, 563 cm ; MS (EI) m/z: 819.8 (M ). Anal.
calcd for C53H30N8: C 77.71, H 8.61, N 13.68; found C
77.63, H 8.60, N 13.14.
Compound 8 1H NMR (CDCl3, 300 MHz) δ: 8.59
＋
1
756, 721, 563 cm ; MS (EI) m/z: 763.3 (M ). Anal.
calcd for C46H66N8O2: C 72.40, H 8.72, N 14.68; found
C 72.53, H 9.14, N 14.18.
(d, J＝4.5 Hz, 3H), 7.86 (s, 3H), 7.69 (t, J＝9.0 Hz, 6H),
7.28—7.20 (m, 9H), 7.14 (d, J＝8.1 Hz, 6H), 5.68 (s,
6H); 13C NMR (CDCl3, 300 MHz) δ: 55.9, 120.0, 122.6,
123.7, 124.6, 125.6, 127.0, 137.6, 147.4, 148.1, 150.0,
Compound 6a 1H NMR (CDCl3, 400 MHz) δ:
8.62 (d, J＝4.4 Hz, 2H), 8.52 (s, 2H), 7.96—7.94 (m,
4H), 7.66 (t, J＝6.0 Hz, 2H), 7.37 (d, J＝8.8 Hz, 2H),
7.28—7.22 (m, 4H), 5.74 (s, 4H), 4.22 (t, J＝5.4 Hz,
154.8; IR (KBr) ν: 3136, 3100, 3049, 3004, 2946, 1609,
1558, 1494, 1458, 1434, 1358, 1322, 1282, 1225, 1187,
－1
1077, 1049, 974, 837, 755, 723, 598, 543 cm . Anal.
Chin. J. Chem. 2010, 28, 2226—2232
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
2231

Fu et al.
FULL PAPER
calcd for C44H33N13: C 70.08, H 4.62, N 25.30; found C
69.72, H 4.76, N 25.01.
3210.
6
7
Schuster, E. M.; Botoshansky, M.; Gandelman, M. Angew.
Chem., Int. Ed. 2008, 47, 4555.
Schulze, B.; Friebe, C.; Hager, M. D.; Winter, A.;
Hoogenboom, R.; Gorls, H.; Schubert, U. S. Dalton Trans.
2009, 787.
Struthers, H.; Spingler, B.; Mindt, T. L.; Schibli, R. Chem.
Eur. J. 2008, 14, 6173.
Mindt, T. L.; Müller, C.; Melis, M.; de Jong, M.; Schibli, R.
Bioconjugate Chem. 2008, 19, 1689.
Complex Cu(II)-3a and Cu(II)-3c The complex
Cu(II)-3a was obtained from a layered method by care-
fully adding methanol solution of CuCl2•2H2O onto a
CH2Cl2 solution of 3a. Blue crystals. IR (KBr) ν: 3118,
3094, 3068, 3034, 2996, 1639, 1607, 1574, 1485, 1438,
1356, 1316, 1227, 1194, 1156, 1073,－1056, 1025, 972,
8
9
1
831, 764, 720, 697, 605, 516, 477 cm . Anal. calcd for
C28H24Cl2CuN8: C 55.40, H 3.99, N 18.46; found C
55.53, H 4.38, N 18.35.
10 Mindt, T. L.; Struthers, H.; Brans, L.; Anguelov, T.;
Schweinsberg, C.; Maes, V.; Tourwe, D.; Schibli, R. J. Am.
Chem. Soc. 2006, 128, 15096.
11 Maisonial, A.; Serafin, P.; Traïkia, M.; Debiton, E.; Théry,
V.; Aitken, D. J.; Lemoine, P.; Viossat, B.; Gautier, A. Eur.
J. Inorg. Chem. 2008, 298.
Complex Cu (II)-3c was synthesized as in Cu(II)-3c.
Blue crystals. IR (KBr) ν: 3126, 3085, 3030, 2921, 1618,
1518, 1463, 1429, 1358, 1319, 1228, 1191, 1146, 1074,
1047, 9－67, 909, 858, 810, 767, 720, 694, 611, 551, 490,
1
461 cm . Anal. calcd for C84H72Cl6Cu3N24: C 55.40, H
3.99, N 18.46; found C 54.80, H 3.99, N 18.49.
12 Beyer, B.; Ulbricht, C.; Escudero, D.; Friebe, C.; Winter, A.;
Gonzalez, L.; Schubert, U. S. Organometallics 2009, 28,
5478.
13 Bastero, A.; Font, D.; Pericas, M. A. J. Org. Chem. 2007,
72, 2460.
14 Spencer, L. P.; Altwer, R.; Wei, P.; Gelmini, L.; Gauld, J.;
Stephan, D. W. Organometallics 2003, 22, 3841.
15 Zou, L.; Fu, Y.; Yan, X.; Chen, X.; Qin, J. J. Polym. Sci.
Part A: Polym. Chem. 2007, 46, 702.
Complex Co(II)-3a The product had been grown
by a layered method, in which the layered CoCl2 ace-
tone solution was onto an acetone solution of 3a.
Red-purple crystals. IR (KBr) ν: 3135, 3057, 2983, 2935,
1654, 1606, 1574, 1481, 1437, 1359, 1322, 1234, 1201,
1161, 1086, 1065, 1020, 975, 831, 766, 719, 697, 663,
－1
611, 511, 479 cm . Anal. calcd for C28H24N8Cl2Co: C
55.83, H 4.02, N 18.60; found C 55.71, H 3.92, N 18.27.
16 Crystallographic data for Cu(II)-3c, Co(II)-3a and 5a have
been deposited with the Cambridge Crystallographic Data
Centre as supplementary materials with the number CCDC
777713, 759810 and 759811. These data can be obtained
free of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
17 Crowley, J. D.; Bandeen, P. H.; Hanton, L. R. Polyhedron
2010, 29, 70. When we prepared this manuscript, the com-
plex Cu(II)-3a had been reported in this reference. But in
their work the Cu—N(2) distance was 2.693(2) Å and
2.672(2) Å, repectively, which has a little difference from
the data in this work.
References and note
1
2
Gavrilova, A. L.; Bosnich, B. Chem. Rev. 2004, 104, 349.
Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K.
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Himo, F.; Lovell, T.; Hilgraf, R.; Rostovtsev, V. V.; Noo-
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5
Lutz, J. F. Angew. Chem., Int. Ed. 2007, 46, 1018.
van Assema, S. G. A.; Tazelaar, C. G. J.; de Jong, G. B.;
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2232
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© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 2226—2232