Syntheses, structures, and characterizations of three Ag(I) complexes constructed by length-modulated pyrazole-based ligands

Article abstract of DOI:10.1080/00958972.2013.840774

Three coordination complexes with N-donor ligands, Ag2(L1)1.5(NO3)2 (1), Ag3(L2)2(NO3)3 (2), and Ag(L1)2NO3 (3) {L1 = 1,4-bis(pyrazole-1-ylmethyl) benzene, L2 = 4,4′-bis(pyrazole-1-ylmethyl)biphenyl}, have been synthesized and structurally characterized by elemental analysis, IR spectroscopy, TGA, and X-ray single crystal diffraction. Complex 1 shows a 3-D fsh-3,4-P21/c structure with brevity code {8³}²{8 ⁵·10}. Complex 2 has a 3-D framework with a 2-D layer penetrated by an infinite 1-D zigzag chain. Complex 3 exhibits a (4,4)-net racemizing layer structure with nitrate anions filling the cavity. The results indicate that L1 and L2 can adopt varied conformations in formation of the complexes, and the length of the ligands plays a key role in configuring and directing the corresponding structure of the complexes.

Full text of DOI:10.1080/00958972.2013.840774

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Syntheses, structures, and
characterizations of three Ag(I)
complexes constructed by length-
modulated pyrazole-based ligands
Guang-Feng Houa, Ying-Hui Yuab, Xue Wanga, Jin-Sheng Gaoab, Bo
Wena, Xiao-Dan Wanga & Peng-Fei Yana
a Engineering Research Center of Pesticide of Heilongjiang
University, Heilongjiang University, Harbin, China
b School of Chemistry and Materials Science, Heilongjiang
University, Harbin, China
Accepted author version posted online: 05 Sep 2013.Published
online: 02 Oct 2013.
To cite this article: Guang-Feng Hou, Ying-Hui Yu, Xue Wang, Jin-Sheng Gao, Bo Wen, Xiao-Dan
Wang & Peng-Fei Yan (2013) Syntheses, structures, and characterizations of three Ag(I) complexes
constructed by length-modulated pyrazole-based ligands, Journal of Coordination Chemistry, 66:19,
3402-3411, DOI: 10.1080/00958972.2013.840774
To link to this article: http://dx.doi.org/10.1080/00958972.2013.840774
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Journal of Coordination Chemistry, 2013
Vol. 66, No. 19, 3402–3411, http://dx.doi.org/10.1080/00958972.2013.840774
Syntheses, structures, and characterizations of three Ag(I)
complexes constructed by length-modulated pyrazole-based
ligands
GUANG-FENG HOU†, YING-HUI YU†‡, XUE WANG†, JIN-SHENG GAO*†‡,
BO WEN†, XIAO-DAN WANG† and PENG-FEI YAN†
†Engineering Research Center of Pesticide of Heilongjiang University, Heilongjiang University,
Harbin, China
‡School of Chemistry and Materials Science, Heilongjiang University, Harbin, China
(Received 15 September 2012; accepted 5 August 2013)
Three coordination complexes with N-donor ligands, Ag2(L1)1.5(NO3)2 (1), Ag3(L2)2(NO3)3 (2),
and Ag(L1)2NO3 (3) {L1 = 1,4-bis(pyrazole-1-ylmethyl)benzene, L2 = 4,4′-bis(pyrazole-1-ylmethyl)
biphenyl}, have been synthesized and structurally characterized by elemental analysis, IR spectros-
copy, TGA, and X-ray single crystal diffraction. Complex 1 shows a 3-D fsh-3,4-P21/c structure
with brevity code {83}2{85·10}. Complex 2 has a 3-D framework with a 2-D layer penetrated by an
infinite 1-D zigzag chain. Complex 3 exhibits a (4,4)-net racemizing layer structure with nitrate
anions filling the cavity. The results indicate that L1 and L2 can adopt varied conformations in for-
mation of the complexes, and the length of the ligands plays a key role in configuring and directing
the corresponding structure of the complexes.
Keywords: Ag(I) complex; Crystal structure; Length-modulated ligand
1. Introduction
Design and construction of metal-organic coordination frameworks are of interest due to
their structural diversity and potential applications in heterogeneous catalysis, molecular
recognition, magnetism, gas storage, ion exchange, nonlinear optics, and electrical conduc-
tivity [1–4]. N-containing ligands, such as imidazole and pyrazole derivatives, play an
important role because of their good coordination and ability to transmit electronic effects
[5–8]. One example is 1,4-bis(imidazol-1-ylmethyl)benzene (bix) consisting of a rigid
phenyl linking two coordinated groups via flexible methylene sp3-carbons. Such structural
feature endows semi-rigidity to bix, which could construct discrete metallomacrocycles,
1-D infinite chains, 2-D polyrotaxane networks, and 3-D frameworks when reacting with
metal ions [9–13]. Previous research also shows that bix is particularly useful in formation
of interpenetrating networks [14], catenanes [15], and polyrotaxanes [16]. As a sequel to
our continuing efforts in exploring the influence of ligands with different coordination sites
*Corresponding author. Email: gaojins@hlju.edu.cn
© 2013 Taylor & Francis

Ag(I) with pyrazole-based ligands
3403
on the structures of coordination polymers [17], we change imidazole groups in bix to
pyrazole groups obtaining 1,4-bis(pyrazol-1-ylmethy)benzene (L1) to tune the coordination
direction and conformation of the ligand, which may lead to new coordination complexes.
Thus far, a series of polyoxometalates (POMs) supported L1 and CuI complexes were
reported, showing 0D to 3-D structure and bearing surface photovoltaic and electrochemical
properties [18]. We also synthesized 4,4′-bis(pyrazole-1-ylmethyl)biphenyl (L2) to
investigate the effect of ligand length on the structures of their coordination complexes
(scheme 1).
These two pyrazole-containing ligands have flexibility and rigidity in coordinating as the
building blocks, which makes it possible to take trans- or cis-conformations. Furthermore,
different spacers give different molecular length, which may fulfill the expectation of
obtaining different crystal configurations. However, formation of inorganic–organic
supramolecules is influenced by factors such as the geometry of metal ions, the nature of
ligands, counterions, the ratio of metal salt and ligand, and solvent system or templates.
Thus, understanding how these considerations affect metal coordination and crystal packing
is at the forefront of controlling coordination supramolecular arrays.
Herein, we report the crystal structures of three complexes obtained from the reaction of
AgNO3 with L1 and L2: {[Ag2(L1)1.5(NO3)2]}n (1) is a 3-D framework; {[Ag3(L2)2
(NO3)3]}n (2) shows a penetrated supramolecular structure consisting of 1D coordination
motifs interpenetrating a 2-D layer; by changing the molar ratio of ligand and AgI, we
obtained {[Ag(L1)2(NO3)]}n (3) which is an enantiomeric layer structure. All complexes
were characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR
analysis, and thermal gravimetric analysis (TGA).
2. Experimental
2.1. Materials and methods
Commercial chemicals were of reagent grade and used as received. Elemental analyses were
performed on a CARLO ERBA 1106 analyzer. IR spectra were recorded on a Bruker IFS
Scheme 1. Schematic representation of 1,4-bis(pyrazole-1-ylmethyl)benzene (L1) and 4,4′-bis(pyrazole-1-ylmethyl)
biphenyl (L2).

3404
G.-F. Hou et al.
66v FT-IR spectrometer equipped with a DGTS detector (32 scans) by using KBr pellets.
1H NMR spectra were performed on a Bruker AV 300 MHz spectrometer. Thermogravimet-
ric measurements were done on a Perkin–Elmer TGA 7 analyzer.
2.2. Preparation of L1 and L2
L1 and L2 were synthesized using an improved method described elsewhere [19]. A
mixture of pyrazole (9.0 g, 130 mM) and NaOH (5.5 g, 130 mM) in DMSO (40 mL) was
stirred at 50 °C for 1 h and 1,4-bis(chloro)benzene (10.50 g, 60 mM) for L1 or 4,4′-bis
(chloro)bibenzene (15.06 g, 60 mM) for L2 in DMSO (60 mL) was added. The mixture
was cooled to room temperature after being stirred at 60 °C for 24 h and poured into
200 mL water. White solid that formed immediately was isolated by filtration and then
dried in air (L1: 10.8 g, 75% yield; L2: 11.8 g, 82% yield). Elemental analysis: Calcd
for L1-C14H14N4: C, 70.57; H, 5.92; N, 23.51%. Found: C, 70.41; H, 5.79; N, 23.80%.
IR (KBr, cm−1): 3116 (m), 2934 (w), 2857 (w), 1812 (w), 1759 (w), 1516 (s), 1451 (s),
1424 (s), 1398 (s), 1357 (s), 1284 (s), 1229 (s), 1092 (s), 1050 (s), 958 (s), 807 (s),
1
762 (s), 744 (s), 615 (m), 483 (s). H NMR (CDCl3): 5.29 (2H, s, CH2), 6.27 (1H, t),
7.17 (2H, d), 7.36 (1H, d), 7.53 (1H, d). Elemental analysis: Calcd for L2-C20H18N4: C,
76.41; H, 5.77; N, 17.82%. Found: C, 76.78; H, 5.50; N, 17.72%. IR (KBr, cm−1):
3113 (w), 2933 (w), 1638 (w), 1515 (m), 1441 (m), 1397 (s), 1281 (m), 1094 (m),
1054 (m), 970 (m), 837 (m), 802 (m), 758 (s), 750 (s), 623 (m). 1H NMR (CDCl3):
5.37 (2H, s, CH2), 6.31 (1H, t), 7.27 (2H, d), 7.43 (1H, d), 7.52 (2H, d), 7.57 (1H, d).
2.3. Syntheses of 1–3
2.3.1. Synthesis of [Ag2(L1)1.5(NO3)2] (1). An aqueous solution (5 mL) of AgNO3
(17.0 mg, 0.1 mM) was added slowly with constant stirring to an acetonitrile solution (5 mL)
of L1 (23.8 mg, 0.1 mM) to give a clear solution. The mixture was heated to 50 °C and stirred
for 1 h. After filtration, colorless blocks suitable for X-ray diffraction were obtained in 37%
yield by slow evaporation at room temperature for several days. Elemental analysis: Calcd
for C21H21N8Ag2O6: C, 36.18; H, 3.04; N, 16.07%. Found: C, 36.15; H, 3.13; N, 16.14%. IR
(KBr, cm−1): 3434 (s), 3109 (w), 1634 (m), 1517 (m), 1384 (s), 1340 (s), 1162 (m),
1059 (m), 1019 (w), 974 (m), 829 (w), 775 (s), 616 (m).
2.3.2. Synthesis of [Ag3(L2)2(NO3)3] (2). Complex 2 was obtained in 47% yield by
procedure similar to the synthesis of 1 except that L2 (31.4 mg, 0.1 mM) was used instead
of L1. Elemental analysis: Calcd for C40H36Ag3N11O9: C, 42.20; H, 3.19; N, 13.53%.
Found: C, 42.11; H, 3.29; N, 13.54%. IR (KBr, cm−1): 3435 (s), 3109 (w), 1635 (m),
1517 (m), 1385 (s), 1340 (s), 1162 (w), 1102 (m), 1019 (w), 974 (m), 829 (w), 775 (s),
616 (m).
2.3.3. Synthesis of [Ag(L1)2(NO3)] (3). Complex 3 was obtained in 42% yield by
procedure similar to the synthesis of 1 except that more L1 (47.6 mg, 0.2 mM) was used.
Elemental analysis: Calcd for C28H28AgN9O3: C, 42.20; H, 3.19; N, 13.53%. Found: C,
42.11; H, 3.09; N, 13.51%. IR (KBr, cm−1): 3428 (s), 3109 (w), 1628 (m), 1517 (m),
1385 (s), 1340 (s), 1163 (w), 1102 (m), 1059 (w), 977 (w), 762 (m), 617 (m).

Ag(I) with pyrazole-based ligands
3405
2.4. X-ray Crystallography
Single-crystal X-ray diffraction data for 1–3 were collected on a Rigaku R-AXIS RAPID
imaging plate diffractometer with graphite-monochromated Mo Kα (λ = 0.71073 Å) radia-
tion at 291 K. Empirical absorption corrections based on equivalent reflections were
applied. The structures of 1–3 were solved by direct methods and refined by full-matrix
least-squares on F2 using SHELXS-97 crystallographic software package [20]. All non-
hydrogen atoms were refined anisotropically. Hydrogens bound to carbons were placed in
calculated positions and treated as riding on their parent with C−H = 0.93 Å (aromatic) or
0.97 Å (methylene), and with Uiso (H) = 1.2 Ueq (C). The nitrates in 2 are disordered, with
one nitrate disordered over two positions with occupancies of 0.5 for each position, while
two oxygens in the other nitrate are also disordered over two positions with occupancies of
0.5 for each position. One nitrate in 3 is disordered, with two O disordered over two
positions and refined occupancies of 0.55(2), 0.45(2), 0.48(1) and 0.52(1) for O1, O1′, O2
and O2′, respectively. Crystal parameters, data collections and refinement results for 1–3 are
summarized in table 1. Crystallographic data have been deposited to the Cambridge Crystal-
lographic Data Centre with the deposition numbers CCDC 735295, 738533, and 746818
for 1–3, respectively.
3. Results and discussion
3.1. Crystal structure descriptions
To investigate the influence of bridging ligands with different lengths on the formation of
supramolecular architectures, L1 with phenyl linker and L2 with biphenyl linker are
selected to react with AgNO3.
Table 1. Crystal data and structure refinements for 1–3.
1
2
3
Empirical formula
Fw
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
C
21H21N8Ag2O6
C40H36Ag3N11O9
1138.41
Triclinic
P ī
8.3484(17)
9.5230(19)
14.903(3)
90.22(3)
104.12(3)
112.79(3)
1031.7(4)
1
C28H28AgN9O3
646.46
Monoclinic
C c
14.749(3)
14.332(3)
13.346(3)
90
97.06(3)
90
2799.9(10)
4
697.20
Monoclinic
P21/c
10.035(2)
6.481(3)
16.114(5)
90
113.84(2)
90
2437.7(10)
4
γ (°)
V (Å3)
Z
DCalcd (g cm–3
)
1.900
1.662
1380
1.832
1.480
566
1.534
0.768
1320
μ (mm–1
F(000)
)
Collected/unique
R(int)
23,147/5551
0.0283
1.026
0.0312
0.0755
0.0392
0.0791
8199/3612
0.0296
1.090
0.0501
0.1554
13,376/6062
0.0209
1.016
0.0315
0.0810
0.0373
0.0839
GOF on F2
Rla[I > 2σ(I )]
wR2b[I > σ(I )]
Rla(all)
0.0690
0.1751
wR2b (all)
aR1 = (Σ||Fo| – |Fc|)/Σ|Fo|.
bwR2 = [Σw(Fo2 – Fc2)2/Σw(Fo2)2]1/2
.

3406
G.-F. Hou et al.
3.1.1. Complex 1. Single-crystal X-ray diffraction analysis shows that the asymmetric unit
of 1 consists of two AgI cations, two NO3 , one full and one half L1. As shown in figure 1a,
–
there are three crystallographically unique AgI cations, with different coordination spheres.
Ag1 is a T-shaped coordination environment connected with two N from two pyrazoles and
one O from nitrate. Ag–N bond distances are 2.156(2)–2.164(2) Å, Ag1–O bond distance is
2.720(3) Å and the N–Ag–N coordination angle is 172.29(9) (table 2). However, Ag2 is
five-coordinate in a tetragonal pyramid, connected with one N from L1 and four O from two
nitrates; the Ag2–O bond distances are 2.337(3) –2.646(3) Å and the Ag2–N bond distance
is 2.210(3) Å (table 2). Two Ag2 ions are connected by two nitrates to form a dimer with
Ag2 Ag2I distance of 4.04 Å. L1 links Ag1 to Ag2 with cis- and Ag1 to Ag1 with
Figure 1. (a) Molecule structure of 1 with the ellipsoids drawn at the 50% probability level, where hydrogens are
omitted for clarity; (b) 1D helical chain structure of 1; (c) Schematic illustration of 3D fsh-3,4-P21/c structure with
the brevity code {83}2{85.10}. Symmetry codes: (I) 1 – x, –1 – y, 1 – z; (II) –x, 0.5 + y, 0.5 – z; (III) –x, – y, 1 – z.

Ag(I) with pyrazole-based ligands
3407
trans-conformation constructing a 1-D zigzag chain (figure 1b). A 3-D framework is
constructed by Ag1 Ag2 (3.245(1) Å) and Ag O (2.720 (3) Å) weak interactions between
adjacent chains. Topological analysis indicates a 3-D fsh-3,4-P21/c structure with brevity
code {83}2{85·10} when the Ag2O2 dimer is reduced to a four connected node (figure 1c).
Ag–Ag or Ag–O weak interactions play an important role in the packing structure, which
have been well documented [21].
3.1.2. Complex 2. To evaluate the influence of the length of ligand on the product struc-
ture, L2 with longer spacer is used to synthesize 2. Single-crystal X-ray diffraction analysis
reveals that 2 crystallizes in the triclinic system with P ī space group. The asymmetric unit
of 2 consists of two crystallographically independent AgI cations, two NO3–, and two half
L2 (figure 2a). In 2, Ag1 is in a disordered coordination environment with Ag–O bond dis-
tance from 2.400(12) to 2.467(12) Å and the Ag–N bond distance of 2.207(5) Å (table 2).
These bond distances are consistent with reported values of Ag–N-containing complexes
[22]. Two adjacent Ag1 are linked by weak Ag1–O1 (2.799(1) Å) coordination interaction
to form dimers with Ag·Ag distance of 6.090(2) Å. These dimers are linked by other
nitrates and trans-conformation L2 to form a 2D square grid with large cavities of approxi-
mately 13.07 × 8.35 Å2 (figure 2b). However, Ag2 is two coordinate by two trans-confor-
mation L2 [N(3)#2–Ag(2)–N(3) 180.00°] to build up a zigzag chain. Interestingly, these
Table 2. Selected bond lengths and angles for 1–3.
Complex 1
Ag(1)−N(5)
2.156(2)
2.720(3)
2.337(3)
2.545(2)
3.245(1)
172.29(9)
90.48(9)
92.60(9)
95.15(9)
113.31(9)
130.95(10)
Ag(1)−N(7)
Ag(2)−N(3)
Ag(2)−O(1)
Ag(2)−O(5)
2.164(2)
2.210(3)
2.529(2)
2.646(3)
Ag(1)−O(3)II
Ag(2)−O(4)
Ag(2)−O(1)I
Ag(1)−Ag(2)II
N(5)−Ag(1)−N(7)
N(7)−Ag(1)−O(3)II
N(3)−Ag(2)−O(1)
N(3)−Ag(2)−O(1)I
N(3)−Ag(2)−O(5)
O(1)−Ag(2)−O(5)
N(5)−Ag(1)−O(3)II
N(3)−Ag(2)−O(4)
O(4)−Ag(2)−O(1)
O(1)−Ag(2)−O(1)I
O(4)−Ag(2)−O(5)
O(1)#2−Ag(2)−O(5)
97.07(9)
156.81(10)
110.55(9)
74.45(8)
49.87(8)
137.87(8)
Symmetry codes: I: −x + 1, −y − 1, −z + 1; II: −x, y + 1/2, −z + 1/2
Complex 2
Ag(1)−N(1)
Ag(1)−O(7)
Ag(1)−O(2)
N(1)−Ag(1)−O(1)
O(1)−Ag(1)−O(7)
O(1)−Ag(1)−O(6)III
N(1)−Ag(1)−O(2)
O(7)−Ag(1)−O(2)
N(3)−Ag(1)−N(3)III
2.207(5)
2.467(12)
2.763(10)
143.2(2)
83.0(4)
Ag(1)−O(1)
2.400(12)
2.544(16)
2.129(4)
124.9(3)
114.3(4)
74.8(4)
Ag(1)−O(6)III
Ag(2)−N(3)
N(1)−Ag(1)−O(7)
N(1)−Ag(1)−O(6)III
O(7)−Ag(1)−O(6)III
O(1)−Ag(1)−O(2)
O(6) #1−Ag(1)−O(2)
94.7(5)
116.2(3)
118.8(4)
180.00
46.0(4)
78.2(4)
Symmetry codes: I: −x + 2, −y + 2, −z + 1; II: −x, −y + 1, −z + 1; III: −x + 2, −y + 1, −z; IV: −x + 1, −y + 2, −z + 1
Complex 3
Ag(1)−N(1)
2.304(3)
2.344(3)
116.02(10)
96.61(11)
112.09(10)
Ag(1)−N(5)
2.338(3)
2.414(3)
121.75(10)
100.69(11)
109.97(11)
Ag(1)−N(8)II
Ag(1)−N(4)I
N(1)−Ag(1)−N(5)
N(1)−Ag(1)−N(4)I
N(5)−Ag(1)−N(4)I
N(1)−Ag(1)−N(8)II
N(5)−Ag(1)−N(8)II
N(8)II−Ag(1)−N(4)I
Symmetry codes: I: x + 1/2, y − 1/2, z; II: x + 1/2, y + 1/2, z

3408
G.-F. Hou et al.
zigzag chains penetrate the above-mentioned 2-D square layers to form a 1-D-penetrated
2-D supramolecular framework (figure 2c).
3.1.3. Complex 3. To evaluate the effect of reactant molar ratio in the construction of the
supramolecular architectures, complex 3 is obtained when the ligand/metal ratio increased
from 1 to 2. Single-crystal X-ray diffraction analysis reveals that 3 crystallizes in the
monoclinic system with Cc space group. The asymmetric unit of 3 consists of one AgI, one
–
uncoordinated disordered NO3 , and two L1. As shown in figure 3a, each AgI is four coor-
dinated in tetrahedral geometry defined by four N from four L1 ligands with Ag–N bond
distance from 2.304(3) to 2.414(3) Å (table 2). In 3, two crystallographically independent
L1 both exhibiting cis-conformations bridge AgI to form an undulating 2D (4,4)-net with
each cavity size of 10.283(2) Å × 10.283(2) Å (figure 3b). The uncoordinated nitrates fill
cavities, stabilized by hydrogen bonds (table S1).
Adjacent planes are enantiomers caused by different coordination directions (figure 3c).
Similar phenomena have been found in [Mn(bna)(DMF)2(H2O)2]n∙n(DMF) [23] and {[Cd
(L6)0.5(BIE)(H2O)]∙H2O} [24] [H2bna = 2,2′-dihydroxyl-[1,1′]-binaphthalene3,3′-dicarbox-
ylate acid; H4L6 = 4,4′-oxidiphthalic acid; BIE = 2,2′-bis(1H-imdazolyl)ether]. We believe
that the sp3-carbon confers a rigid ligand certain flexibility, which probably favors the
Figure 2. (a) Molecule structure of 2 with the ellipsoids drawn at the 50% probability level. (b) 2D network of 2.
(c) View of a topology of 2. Symmetry codes: (I) 2 – x, 2 – y, 1 – z; (II) –x, 1 – y, 1 – z.

Ag(I) with pyrazole-based ligands
3409
Figure 3. (a) Coordination environment of Ag(I) in 3 with the ellipsoids drawn at the 50% probability level; dis-
ordered O atoms of nitrates are omitted for clarity. (b) 2D chiral cavity of 3. (c) Schematic illustration of stacking
structure of 3. Symmetry codes: (I) 0.5 + x, – 0.5 + y, z; (II) 0.5 + x, 0.5 + y, z.
construction of the chiral layer structure. Moreover, distorted coordination sites of N in
pyrazole also increased the possibility of such chiral structure formation.
3.2. Thermal properties
TGA were carried out to examine the thermal stabilities of 1–3. The samples were heated
in flowing N2 with a heating rate of 10 °C min−1. The TGA curves indicate that 1 is stable
to 203 °C, from which point the framework begins to collapse. The observed final mass
remnant of 27.21% is ascribed to deposition of Ag2O (Calcd: 32.09%). However, 2 and 3
show the weight loss from beginning, caused by loss of adsorbed water. Complexes 2 and 3
are stable to 220 and 240 °C, respectively, from which point the frameworks begin to
collapse, and the residues may be ascribed to Ag2O.

3410
G.-F. Hou et al.
4. Conclusions
Three inorganic–organic complexes 1–3 have been synthesized and characterized, and their
structural relationships with the reaction conditions were investigated. Results reveal that
the ligand and reactant molar ratio have effects on controlling the structures of coordination
complexes: (i) Complexes 1 and 2 were synthesized at the same conditions except that
ligands with different lengths are used. Complex 1 exhibits a 3D fsh-3,4-P21/c structure
constructed by L1, while 2 shows a 1D-penetrated 2D structure owning to the large cavity
formed by longer L2. (ii) Complex 1 was synthesized in 1 : 1 M ratio (metal : ligand), in
which Ag is coordinated with two L1; in contrast to that, 3 was synthesized in 1 : 2 M ratio,
in which Ag is coordinated with four L1. These results could provide promising access to
the rational design and synthesis of metal-organic coordination polymers with specific
structures.
Acknowledgments
We acknowledge the support of the Natural Science Foundation of Heilongjiang Province
(B201108), Scientific Research Fund of Heilongjiang Provincial Education Department
(12531512), and Heilongjiang University.
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