Article

pubs.acs.org/crystal

Synthesis, Crystal Structure, and Luminescence of Zn/Cd

Coordination Polymers with a New Fuctionalized Terpyridyl
Carboxylate Ligand
Bing Xu, Juan Xie, Huai-Ming Hu,* Xiao-Le Yang, Fa-Xin Dong, Meng-Lin Yang, and Gang-Lin Xue
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and
Materials Science, Northwest University, Xi’an 710069, China
*
S Supporting Information

ABSTRACT: Eight new coordination polymers, [Zn(L)Cl]n (1),

[Zn2(L)4]n·2nH2O (2), [Zn2(L)2(1,3-bdc)]n (3), [Zn2(L)(1,3-bdc)-
(OH)] n ·0.5nH 2 O (4), [Zn 9 (L) 4 (1,3-bdc) 6 (OH) 2 ] n ·3nH 2 O (5),
[Zn 2 (L) 2 (1,4-bdc)] n ·nH 2 O (6), [Cd 2 (L) 4 ] n ·nH 2 O (7), and
[Cd 3 (L) 2 (1,3-bdc) 2 ] n ·nH 2 O (8) [HL = 4′-(2-carboxyphenyl)-
4,2′:6′,4″-terpyridine, H2(1,3-bdc) = benzene-1,3-dicarboxylic acid,
H2(1,4-bdc) = benzene-1,4-dicarboxylic acid] have been synthesized
under hydrothermal conditions and characterized by elemental analysis,
IR, and single crystal X-ray diffraction. Complexes 1, 2, and 7 display a
two-dimensional (2D) layer structure. Complex 3 presents a
complicated 2D layer structure with paddle-wheel units, which exhibits
an interesting (3,4,6)-connected 3-nodal new topological net with the
point symbol of (3·4·5·62·7)2(3·6·7)2(32·42·52·62·76·8). Complex 4 is a
2-nodal (3,5)-connected 2D bilayer structure with the gek1 topological
net and the point symbol of (3·4·5)(32·4·5·62·74). Complex 5 shows a self-penetrating three-dimensional (3D) framework based
on pentanuclear clusters, which features an intriguing (3,3,4,4,12)-connected 5-nodal new topological net with the point symbol
of (4·62)2(42·64)4(43)2(48·634·822·102). Complex 6 features a 2-fold interpenetrating (3,4)-connected 3D framework with the ins
topological net and the point symbol of (63)(65·8). Complex 8 is a new (4,4,5,6)-connected 3D network built up by a linear
Cd3(COO)6 trinuclear cluster with the point symbol of (42·63·8)2(43·63)2(44·64·82)2(48·66·8). The diverse structures indicate that
rational adjustment of the second ligand, the pH value, and counteranion are good methods to further design metal−organic
compounds with new structures and properties. In addition, the thermal stabilities and photoluminescence properties of 1−8
were also studied.

■ INTRODUCTION
The design and synthesis of metal−organic frameworks
(MOFs) have become a very active area of research, owing
to not only their fascinating topological structures1,2 but also
their promising applications as functional materials in
luminescence, magnetism, absorption, catalysis, ion-exchange,
etc.3−6 Although nowadays there exist a variety of coordination
polymers which possesses fascinating structures and intriguing
properties, it is still a tremendous scientific challenge to predict
and synthesize coordination polymers with expected structures
and properties due to a number of factors that make a big
difference in the formation of MOFs, such as the nature of the
metal center and ligand, reaction medium, metal-to-ligand ratio,
pH value, and counteranion.7−12 Di- and polycarboxylic acids
are widely used as bridging ligands to construct coordination
frameworks with versatile structures.13−17 Meanwhile the
complexes containing multipyridyl ligands have received
much attention in many respects.18−20 At the same time,
unprecedented attention has been paid to d 10 metal
coordination polymers, as a result of their outstanding
photoluminescence.21−23 We are interested in synthesizing
coordination compounds on the basis of multipyridyl ligands
and d10 metal ions and have already made advances in this
field.24−31 Owing to their electronic and steric versatility and
the large π-conjugated structure, 4′-aryl substituted-2,2′:6′,2″-
terpyridine still acts as a kind of classical ligands in coordination
chemistry. Compared with 2,2′:6′,2″-terpyridine, 4,2′:6′,4″-
terpyridine have an advantage that the terminal pyridyl rings
can easily stretch out through the coordination bonds between
nitrogen atoms and metal centers, generating high-dimensional
MOFs. In this regard, Wen and Ke et al. have reported two
porous cadmium(II) frameworks with a polytopic 4-(4-
carboxyphenyl)- 4,2′:6′,4″-terpyridine ligand.32 Due to high
symmetry of this ligand, it enables the formation of
microporous metal−organic frameworks (MMOFs). However,
4′-(2-carboxyphenyl)-4,2′:6′,4″-terpyridine (HL, Scheme 1), as
an asymmetric ligand, is able to generate a series of new
structures, thus, the research system of 4,2′:6′,4″-terpyridine is
Received: November 14, 2013
Revised: January 13, 2014
Published: January 24, 2014

© 2014 American Chemical Society 1629 dx.doi.org/10.1021/cg4016977 | Cryst. Growth Des. 2014, 14, 1629−1641
Crystal Growth & Design
Scheme 1. Schematic Drawing for Ligand HL
enriched. As far as we can see, 4′-(2-carboxyphenyl)-4,2′:6′,4″-
terpyridine has not been reported. It has been selected to
construct new MOFs according to the following factors: (a) HL
is an asymmetric bifunctional polydentate N,O-donor bridging
ligand, which can link adjacent metallic centers through
coordination bonding interactions. The terpyridyl and carbox-
ylate groups can both act as bridging groups, while the
carboxylate group can also serve as a chelating group. (b) HL
has a large π-conjugated structure which markedly makes
contribution to form a better connection between the donor
and acceptor to fulfill electron transport. On the basis of the
above considerations, HL can be extensively employed as a
rigid building block to construct MOFs with remarkable
structures. In this paper, we have synthesized eight new ZnII/
CdII coordination polymers based on HL, namely, [Zn(L)Cl]n
(1), [Zn2(L)4]n·2nH2O (2), [Zn2(L)2(1,3-bdc)]n (3), [Zn2(L)-
(1,3-bdc)(OH)]n·0.5nH2O (4), [Zn9(L)4(1,3-bdc)6(OH)2]n·
3nH2O (5), [Zn2(L)2(1,4-bdc)]n·nH2O (6), [Cd2(L)4]n·nH2O
(7), and [Cd3(L)2(1,3-bdc)2]n·nH2O (8). Meanwhile, their
luminescence properties and thermal stabilities are also studied.
■
EXPERIMENTAL SECTION
All commercially available chemicals and solvents are of reagent grade
and were used as received without further purification. Ligand HL was
synthesized according to the reported procedure with some
modification.33 Infrared spectra were obtained from KBr pellets on a
Bruker EQUINOX 55 Fourier transform Infrared spectrometer in the
400−4000 cm−1 region. Elemental analyses (C, H, and N) were
performed on an elementar Vario EL elemental analyzer. Fluorescence
spectra were recorded on a Hitachi F-4500 spectrophotometer at
room temperature. Thermal gravimetry analyses (TGA) were carried
out with a Universal V2.6 DTA system at a rate of 10 °C/min in a
nitrogen atmosphere. Powder X-ray diffraction (PXRD) measurements
were measured on a Bruker D8 ADVANCE X-ray powder
diffractometer (Cu Kα, 1.5418 Å). The syntheses of complexes 1−8
are shown in Scheme 2.
Preparation of [Zn(L)Cl]n (1). A mixture of ZnCl2 (13.6 mg, 0.1
mmol) and HL (35.3 mg, 0.1 mmol) in H2O (10 mL) was adjusted to
pH = 4 with 0.5 mol L−1 NaOH solution. The mixture were then
placed in a Teflon-lined stainless steel vessel (25 mL) and heated to
180 °C for 72 h. After cooling to room temperature, colorless block
crystals of 1 were obtained. Yield: 30.5 mg, 68% based on Zn. Anal.
Calcd (%) for C22H14ClN3O2Zn2 (453.18): C, 58.30; H, 3.11; N,
9.27%. Found: C, 58.42; H, 3.07; N, 9.28%. IR (KBr, cm−1): 3422 (s),
1616 (s), 1363 (m), 1062 (w), 835 (w), 764 (w), 671 (w), 638 (w).
Preparation of [Zn2(L)4]n·2nH2O (2). A mixture of Zn(Ac)2 (21.9
mg, 0.1 mmol) and HL (35.3 mg, 0.1 mmol) in H2O (10 mL) was
adjusted to pH = 4 with 0.5 mol L−1 NaOH solution. The mixture
were then placed in a Teflon-lined stainless steel vessel (25 mL) and
heated to 180 °C for 72 h. After cooling to room temperature,
colorless quadrate crystals of 2 were obtained. Yield: 29.5 mg, 75.2%
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Scheme 2. Sythesis of Complexes 1−8
based on Zn. Anal. Calcd (%) for C88H56N12O10Zn2 (1572.19): C,
67.23; H, 3.59; N, 10.69%. Found: C, 67.32; H, 3.64; N, 10.65%. IR
(KBr, cm−1): 3423 (s), 1616 (s), 1363(m), 1064 (w), 835 (w), 764
(w), 638 (w).
Preparation of [Zn2(L)2(1,3-bdc)] n (3). Complex 3 was
synthesized in a similar procedure as 1, except that the metal salt
was replaced by Zn(Ac)2·2H2O (21.9 mg, 0.1 mmol) and H2(1,3-bdc)
(16.6 mg, 0.1 mmol) was introduced into the reaction system.
Colorless quadrate crystals of 3 were obtained. Yield: 34.63 mg, 69.3%
based on Zn. Anal. Calcd (%) for C52H32N6O8Zn2 (999.58): C, 62.48;
H, 3.23; N, 8.41%. Found: C, 62.59; H, 3.24; N, 8.46%. IR (KBr,
cm−1): 3421 (s), 2926 (w), 1616 (m), 1557 (m), 1501 (m), 1394 (s),
1047 (w), 940 (w), 833 (w), 740 (w), 532 (w), 472 (w).
Preparation of [Zn2(L)(1,3-bdc)(OH)]n·0.5nH2O (4). A mixture
of Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol), HL (35.3 mg, 0.1 mmol),
and H2(1,3-bdc) (16.6 mg, 0.1 mmol) in H2O (10 mL) was adjusted
to pH = 7 with 0.5 mol L−1 NaOH solution. The mixture were then
placed in a Teflon-lined stainless steel vessel (25 mL), heated to 180
°C for 72 h. After cooling to room temperature, colorless block
crystals of 4 were obtained. Yield: 25.5 mg, 75.8% based on Zn. Anal.
Calcd (%) for C30H19N3O7.5Zn2 (672.22): C, 54.60; H, 2.85; N,
6.25%. Found: C, 54.58; H, 2.83; N, 6.28%. IR (KBr, cm−1): 3421 (s),
3062 (w), 1611 (s), 1564 (m), 1407 (s), 1064 (s), 940 (w), 836 (w),
731 (w), 649 (w), 515 (w).
Preparation of [Zn9(L)4(1,3-bdc)6(OH)2] n·3nH2O (5). Complex
5 was obtained by the same procedure used for preparation of 4,
except that the pH value of the reaction mixture was adjusted to 5
instead of 7. Colorless prism crystals of 5 were obtained. Yield: 26.8
mg, 77.8% based on Zn. Anal. Calcd (%) for C136H86N12O39Zn9
(3100.5): C, 52.68; H, 2.80; N, 5.42%. Found: C, 52.72; H, 2.91; N,
5.57%. IR (KBr, cm−1): 3427 (s), 3062 (w), 1616 (s), 1564 (m), 1409
(m), 1064 (w), 836 (w), 748 (w), 650 (w), 520 (w) .
Preparation of [Zn2(L)2(1,4-bdc)]n·nH2O (6). Complex 6 was
synthesized in a similar procedure as 5, except that H2(1,4-bdc) was
used as the auxiliary ligand instead of H2(1,3-bdc). Colorless block
crystals of 6 were obtained. Yield: 38.4 mg, 75.4% based on Zn. Anal.
Calcd (%) for C52 H34 N6 O9 Zn2 (1017.59): C, 61.37; H, 3.37; N,
8.26%. Found: C, 61.38; H, 3.40; N, 8.28%. IR (KBr, cm−1): 3543 (s),
2926 (w), 1573 (s), 1501 (m), 1405 (s), 901 (m), 788 (m), 723 (m),
556 (m).
Preparation of [Cd2(L)4]n·nH2O (7). A mixture of CdCl2·2.5H2O
(11.4 mg, 0.05 mmol) and HL (17.6 mg, 0.05 mmol) in H2O (10 mL)
was adjusted to pH = 5 with the 0.5 mol L−1 NaOH solution. The
mixture were then placed in a Teflon-lined stainless steel vessel (25
mL) and heated to 180 °C for 72 h. After cooling to room
temperature, colorless quadrate crystals of 2 were obtained. Yield: 29.3
mg, 71% based on HL. Anal. Calcd (%) for C88H56Cd2N12O9
(1650.25): C, 61.37; H, 3.37; N, 8.26%. Found: C, 61.38; H, 3.40;
dx.doi.org/10.1021/cg4016977 | Cryst. Growth Des. 2014, 14, 1629−1641
Crystal Growth & Design Article

Table 1. Crystal Data and Structural Refinement Parameters for 1−8

compound 1 2 3 4
empirical formula C22H14ClN3O2Zn C88H56N12O10Zn2 C52H32N6O8Zn2 C30H19N3O7.5Zn2
formula weight 453.18 1572.19 999.58 672.22
crystal system monoclinic triclinic triclinic monoclinic
space group P2(1)/n P1̅ P1̅ C2/c
a (Å) 12.1335(11) 11.5711(9) 12.4642(19) 23.798(8)
b (Å) 7.9711(7) 12.1705(9) 12.5823(17) 19.705(8)
c (Å) 20.3084(19) 14.5802(19) 15.269(2) 13.445(5)
α (deg) 90 98.625(2) 104.357(2) 90
β (deg) 97.4430(10) 94.455(2) 108.967(2) 112.564(8)
γ (deg) 90 116.5010(10) 90.771(3) 90
V (Å3) 1947.6(3) 1792.3(3) 2182.2(5) 5822(3)
Z 4 1 2 8
ρcalcd (g·cm−3) 1.546 1.457 1.521 1.534
μ (mm−1) 1.422 0.744 1.165 1.701
F(000) 920 808 1020 2720
reflections collected 9551 9141 11124 14522
reflections unique 3452 6281 7653 5160
R(int) 0.0236 0.0196 0.046 0.0393
parameters 262 514 613 391
S on F2 1.035 1.038 1.046 1.050
R1, wR2 [I > 2σ(I)] 0.0301, 0.0727 0.0462, 0.1036 0.0756, 0.1281 0.0402, 0.1049
R1, wR2 (all data) 0.0408, 0.0792 0.0635, 0.1129 0.1129, 0.1463 0.0537, 0.1118
Δρmax and min (e Å−3) 0.309 and −0.231 0.502 and −0.442 0.545 and −0.455 0.682 and −0.327
5 6 7 8
empirical formula C136H86N12O39Zn9 C52H34N6O9Zn2 C88H56Cd2N12O9 C60H36Cd3N6O12
formula weight 3100.5 1017.59 1650.25 1370.15
crystal system triclinic monoclinic triclinic monoclinic
space group P1̅ P2/n P1̅ P2(1)/n
a (Å) 14.198(3) 12.5807(16) 11.605(2) 14.896(3)
b (Å) 14.443(3) 9.3402(12) 12.340(2) 9.8043(17)
c (Å) 18.560(3) 19.104(3) 14.606(4) 17.559(3)
α (deg) 67.524(3) 90 99.002(3) 90
β (deg) 71.377(3) 103.775(3) 96.346(4) 93.155(3)
γ (deg) 65.820(3) 90 116.734(2) 90
V (Å3) 3147.9(10) 2180.2(5) 1805.9(7) 2560.4(8)
Z 1 2 1 2
ρcalcd (g cm−3) 1.636 1.55 1.517 1.777
μ (mm−1) 1.775 1.17 0.661 1.309
F(000) 1568 1040 836 1356
reflections collected 15960 10610 9189 12205
reflections unique 11027 3841 6321 4505
R(int) 0.0237 0.0735 0.0160 0.0862
parameters 898 315 505 368
S on F2 1.009 1.017 1.035 0.980
R1, wR2 [I > 2σ(I)] 0.0421, 0.0903 0.0531, 0.1003 0.0314, 0.0709 0.0482, 0.0889
R1, wR2 (all data) 0.0606, 0.0998 0.0925, 0.1159 0.0375, 0.0742 0.1050, 0.1080
Δρmax and min (e Å−3) 0.0631 and −0.602 0.515 and −0.766 0.283 and −0.459 1.131 and −0.801

N, 8.28%. IR (KBr, cm−1): 3423 (s), 1595 (s), 1542 (s), 1396 (s),
1060(w), 832 (m), 763 (m), 537 (w).
Preparation of [Cd3(L)2(1,3-bdc)2]n·nH2O (8). The same
synthetic method as that for 7 was used, except for the introduction
of H2(1,3-bdc) (16.6 mg, 0.1 mmol) into the reaction system.
Colorless block crystals of 8 were obtained. Yield: 36.6 mg, 80.3%
based on Cd. Anal. Calcd (%) for C60H36Cd3N6O12 (1370.15): C,
67.23; H, 3.59; N, 10.69%. Found: C, 67.32; H, 3.64; N, 10.65%. IR
(KBr, cm−1): 3422 (s), 1610 (s), 1563 (m), 1387 (m), 828 (w), 746
(w), 716 (w), 643 (w).
X-ray Crystallography. Intensity data were collected on a Bruker
Smart APEX II CCD diffractometer with graphite-monochromated
Mo Kα radiation (λ = 0.71073 Å) at room temperature. Empirical
absorption corrections were applied using the SADABS program. The
structures were solved by direct methods and refined by the full-matrix
least-squares based on F2 using SHELXTL-97.34 All nonhydrogen
atoms were refined anisotropically and hydrogen atoms of organic
ligands were generated geometrically. Crystal data and structural
refinement parameters for 1−8 are summarized in Table1 and selected
bond distances and bond angles are listed in Table S1 of the
Supporting Information. Crystallographic data have been deposited
with the Cambridge Crystallographic Data Centre, CCDC Nos.
962626−962627 for 1−2, 939307−939309 and 939311 for 3−6, and
962628−962629 for 7−8. These data can be obtained free of charge
via www.ccdc.can.ac.uk/conts/retrieving.html (or from the Cambridge

1631 dx.doi.org/10.1021/cg4016977 | Cryst. Growth Des. 2014, 14, 1629−1641

Crystal Growth & Design
Crystallographic Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.;
fax, (+44) 1223-336033; or e-mail, deposit@ccdc.cam.ac.uk).
■
RESULTS AND DISCUSSION
Crystal Structure of [Zn(L)Cl]n (1). X-ray single-crystal
diffraction analysis reveals that 1 is a two-dimensional (2D)
framework. The asymmetric unit of 1 contains one Zn(II) ion,
one L−, and one Cl− anion. As shown in Figure 1a, Zn1 is
Figure 1. (a) Coordination environment of ZnII ion in 1. The
hydrogen atoms are omitted for clarity (symmetry codes: A = −x, −y,
−z; B = 0.5 + x, 0.5 − y, −0.5 + z). (b) View of the 1D loop chain of 1
along the b axis. (c) View of the 2D layer structure of 1 along the a
axis. (The 1D zigger chain is highlighted.)
surrounded by two nitrogen atoms (N1A and N3B), two
oxygen atoms (O1 and O2) from L− anions, and one chlorine
atom. The coordination geometry can be described as a
distorted trigonal bipyramid geometry with Cl1 and O1 atoms
Scheme 3. Coordination Modes of L− and Auxiliary Ligands in 1−8
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occupying the axial positions [Cl1−Zn1−O1 = 159.21(6)°].
The Zn−O and Zn−N bond lengths are 2.444(2)∼1.986(2) Å
and 2.062(2)∼2.064(2)Å, respectively. The Zn1−Cl1 distance
is 2.2627(8) Å, which is slightly shorter than those reported.35
The three pyridyl rings of L− anion are noncoplanar, and the
terminal pyridyl rings (N1 and N3) are twisted with respect to
the central pyridyl ring (N2) with the dihedral angles of 30.51°
and 28.8°.
Two L− anions adopting a μ3-η1:η1:η2 coordination mode
(Scheme 3, mode I) link two Zn1 ions to form a [Zn2O2N2C18]
24-membered ring containing a type of pore with a size of
8.732 × 12.452 Å based on Zn1···Zn1 and C16···C16. Then the
rings are linked by L− anions to generate a one-dimensional
(1D) loop chain (Figure 1b). These chains are further linked by
the terminal nitrogen atom (N3B) and carboxylate group of L−
anions to give rise to a 2D layer (Figure 1c).
Crystal Structure of [Zn2(L)4]n·2nH2O (2). The X-ray
structural determination indicates that complex 2 is a 2D layer
stucture. The asymmetric unit of 2 consists of one Zn(II) ion,
two L− anions, and one lattice water molecule. As shown in
Figure 2a, Zn1 is five-coordinated by three oxygen atoms (O1,
O3A, and O4A) and two nitrogen atoms (N1B, N4) from four
different L− anions, in which O3A and O4A come from the
chelating carboxylate group of one L− anion. The coordination
geometry of Zn1 can be described as having a distorted trigonal
bipyramidal geometry, in which N4 and O3A atoms occupy the
axial positions [N4−Zn1−O3A = 148.39(11)°]. Zn−O bond
lengths fall in the range of 1.980(2)−2.296(3) Å, and Zn−N
bond lengths are 2.066(3) Å (Zn1−N1B) and 2.071(3) Å
(Zn1−N4), which are in accordance with the previous report.36
Unlike in complex 1, the L− anions adopt two different
coordination fashions: (a) the bimondentate coordination
mode (Scheme 3, mode IV) in which both the carboxylate
group and one terminal pyridyl ring act as a mondentate
coordination mode. (b) The tridentate coordination mode
(Scheme 3, mode II) in which the carboxylate group acts as the
bidentate-chelating coordination mode, and the terpyridyl
moiety acts as the monodentate coordination mode. On the
basis of the connection modes, first, each L− anion with
coordination mode IV join up two Zn(II) ions to form a 1D
zigger chain (Figure 2b). These chains are then further
extended into 2D layer (Figure 2c) through L− anions,
adopting a coordination mode II.
Crystal Structure of [Zn2(L)2(1,3-bdc)]n (3). When
H2(1,3-bdc) was introduced into the reaction system, complex
3 was obtained. X-ray single-crystal diffraction analysis reveals
that 3 is a 2D framework based on paddle-wheel units. The
asymmetric unit of 3 contains two Zn(II) ions, two L−, and one
dx.doi.org/10.1021/cg4016977 | Cryst. Growth Des. 2014, 14, 1629−1641
Crystal Growth & Design
Figure 2. (a) Coordination environment of ZnII ion in 2. The
hydrogen atoms are omitted for clarity (symmetry codes: A = x, 1 + y,
z; B = 1 + x, 1 + y, z). (b) View of the 1D zigger chain of 2. (c) View
of the 2D layer structure of 2. (The 1D zigger chain is highlighted.)
(1,3-bdc)2− anions. As shown in Figure 3a, the environment
around Zn1 can be described as a distorted square-pyramidal
geometry, in which it is coordinated by four oxygen atoms (O1,
O2A, O5, and O6A) from two L− and two (1,3-bdc)2− anions
in an equatorial plane and one nitrogen atom (N4) from L−
anion occupying the axial position. The Zn1−N bond length is
2.023(5) Å, and the Zn1−O distances are in the range of
2.027(4)−2.082(4) Å. Noticeably, the Zn1−O1 [2.034(4) Å]
bond length is similar to the Zn1−O2A [2.030(5) Å] bond
length, which indicates the symmetrical coordination fashion of
the carboxylate in the L− anion. Each Zn2 is coordinated to one
oxygen atom (O3) and two nitrogen atoms (N1, N3B) from
three different L− anions and one oxygen atom (O7C) from a
(1,3-bdc)2− anion, forming a slightly distorted tetrahedral
geometry. It is worth noting that the L− anion adopts two
different coordination modes in 3: (a) the tetradentate
coordination mode in which the carboxylate group adopts the
μ2-bridging coordination mode and the two nitrogen atoms of
two terminal pyridyl rings act as a mondentate coordination
mode (Scheme 3, mode III). (b) The bimondentate
coordination mode in which both the carboxylate group and
the nitrogen atom of one terminal pyridyl ring act as
mondentate coordination modes (scheme 3, mode IV).
Meanwhile, (1,3-bdc)2− anion adopts a μ3-η1:η1:η1-bridging
coordination mode IX (Scheme 3). Two Zn1 ions are bridged
by four carboxylate groups to give a paddle-wheel unit with the
Zn1···Zn1 distance of 2.914(1) Å (Figure 3b). The binuclear
units are then linked by L− anions, adopting coordination mode
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III (Scheme 3) through Zn2−N3 and Zn2−N1 bonds to form
a one-dimensional (1D) loop chain (Figure 3c). Further, these
1D loop chains are cross-linked by (1,3-bdc)2− anions to give
rise to a 2D framework (Figure 3d). Noticeably, L− anions
adopting coordination mode IV (Scheme 3) do not play an
indispensable role in the construction of final 2D framework.
To further understand the structure of 3, the paddle-wheel
Zn(II) unit, L− anion with coodination mode III (Scheme 3)
and Zn2 ion can be regarded as 6-, 3-, and 4-connected nodes,
respectively. Hence, complex 3 possesses a 3-nodal (3,4,6)-
connected network with the point symbol of (3·4·5·62·7)2(3·6·
7)2(32·42·52·62·76·8) (Figure 3e).
Crystal Structure of [Zn2(L)(1,3-bdc)(OH)]n·0.5nH2O
(4). X-ray single crystal diffraction analysis reveals that 4 is a
2D bilayer structure. The asymmetric unit of 4 consists of two
Zn(II) ions, one L−, one (1,3-bdc)2−, and one OH− anion and
half lattice water molecule. As depicted in Figure 4a, Zn1 is five-
coordinated by one nitrogen (N1A) atom and one oxygen
(O1) atom from two L− anions, and three oxygen atoms (O5B,
O6B, and O7) from (1,3-bdc)2− and OH− anions to form a
slightly distorted trigonal bipyramid geometry, in which N1A
and O5B atoms occupy the axial positions [O5B−Zn1−N1A =
150.38(13)°]. Zn2 is four-coordinated by one nitrogen (N3C)
and one oxygen (O2) atoms from two L− anions, and two
oxygen atoms (O3 and O7) from (1,3-bdc)2− and OH− anions
to form a tetrahedral coordination geometry. The Zn−N bond
lengths are 2.046(3) and 2.058(3)Å, and the Zn−O bond
lengths vary from 1.903(3) to 2.152(3)Å, which are consistent
with the corresponding values reported for Zn-pyridyl
compounds.37 The three pyridyl rings of the L− ligand are
nonplanar, each terminal pyridyl group is twisted with respect
to the central one, the dihedral angles between the central and
terminal pyridyl rings are 17.21° (N1 pyridyl ring) and 15.57°
(N3 pyridyl ring), respectively. Interestingly, it can be observed
that Zn1 and Zn2 are connected by an oxgen atom (O7), which
comes from a hydroxyl group. It is worth noting that the
bidentate-bridging carboxylate group of the L− ligand and a μ2-
OH group bridge Zn1 and Zn2 to form a dizinc unit, [Zn2(μ2−
OH)(μ2-O2CR)]. In the dizinc unit, the Zn1···Zn2 separation is
3.299 Å (Figure 4b). In 4, the L− ligand adopts a μ4-η1:η1:η1:η1-
bridging coordination mode III (Scheme 3) and the auxiliary
(1,3-bdc)2− ligand adopts a μ2-η1:η2-bridging coordination
mode VI (Scheme 3). On the basis of these connection modes,
the Zn2 units are linked to generate a 2D staggered bilayer
structure (Figure 4c). To further understand the structure of 4,
the topological analysis was carried out. The L− ligand and
dizinc unit can be regarded as 3- and 5-connected nodes,
respectively. The (1,3-bdc)2− anion is assigned to a linker. On
the basis of the simplification principle,38 complex 4 possesses a
2-nodal (3,5)-connected gek1 net with the point symbol of (3·
4·5)(32·4·5·62·74) (Figure 4d).
Crystal Structure of [Zn9(L)4(1,3-bdc)6(OH)2(H2O)2]n·
3nH2O (5). The crystal structure analysis shows that 5 features
an unusual 3D framework. The asymmetric unit of 5 contains
four and a half Zn(II) ions, two L− anions, three (1,3-bdc)2−
anions, one OH− anion, one coordinated water, and one-and-a-
half lattice water molecules. As shown in Figure 5a, Zn1 is four-
coordinated by one nitrogen atom (N1) from L− ligand and
three oxygen atoms (O5, O9, and O17) from (1,3-bdc)2− and
OH− anions to form a tetrahedral coordination geometry. Zn2
shows a distorted octahedral geometry composed of six oxygen
atoms (O17, O17C, O1A, O1B, O6, and O6C) from two μ3-
OH−, two μ4-L−, and two μ3-(1,3-bdc)2− anions. Zn3 is
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Crystal Growth & Design Article

Figure 3. (a) Coordination environment of ZnII ions in 3. The hydrogen atoms are omitted for clarity (symmetry codes: A = −x + 1, −y, −z + 1; B =
+x, +y − 1, +z; C = +x − 1, +y − 1, +z − 1). (b) The paddle-wheel unit in 3. (c) View of the 1D loop chain of 3 along the a axis. (d) View of the 2D
layer structure of 3. (The 1D zigger chain is highlighted.) (e) Schemetic view of the 2D topology network: the paddle-wheel Zn(II) unit, L− anion
with coodination mode I, and Zn2 ion are marked as blue, green, and red, respectively.

coordinated to one nitrogen atom (N6D) and four oxygen
atoms (O7, O8, O4E, and O18) from two μ4-L−, one μ3-(1,3-
bdc)2− anions, and one coordinated water molecule to show a
distorted trigonal bipyramid geometry, in which O4E and O8
atoms occupy the axial positions [O4E−Zn3−O8 =
163.90(12)°]. Zn4 is bound to one nitrogen atom (N4) from
one μ4-L− anion and five oxygen atoms (O11, O12, O15G,
O16G, and O3F) from one μ4-L− anion and two (1,3-bdc)2−
anions to generate a distorted octahedral coordination
geometry. The coordination environment of Zn5 is penta-
coordinated with a distorted trigonal bipyramid geometry, in
which O14 and O2B atoms occupy the axial positions [O14−
Zn5−O2B = 153.19(12)°]. In 5, two symmetry-related μ3-OH−
groups (symmetry code: −x + 2, −y + 1, −z + 1) connect five
Zn(II) ions to form a [Zn5(μ3-OH−)2]8+ cluster unit, which can
be regarded as two [Zn3(μ3-OH−)2]4+ triangles sharing a
common Zn2 vertex. Such triangles are fit together by four
carboxylate groups to make up the pentanuclear [Zn5(μ3-
OH−)2(COO)4] cluster (Figure 5b), which is similar to some
1634
reported examples.39,40 Therefore, five Zn(II) ions within the
pentanuclear clusters are totally coplanar, in which the Zn···Zn
distances are 3.418 Å (Zn2···Zn5), 3.262 Å (Zn2···Zn1), and
3.522 Å (Zn1···Zn5). Similar to 4, each L− anion adopts μ4-
η1:η1:η1:η1-coordination mode III (Scheme 3) and links two
pentanuclear clusters to generate a 1D loop chain, in which two
Zn1, two Zn5 ions, and two L− anions form a new
{Zn4O4N2C18} 28-member ring, containing a large pore with
a size of ca. 10.063 × 13.212 Å based on the distances of Zn1···
Zn1 and C21···C21. At the same time, a different type of
{Zn2O2N2C18} 24-member ring also emerged, which derives
from two Zn4 atoms and two L− anions containing a type of
pore with size ca. 10.630 × 11.412 Å based on the distances of
Zn4···Zn4 and C38···C38. The two kinds of rings are then
linked by two carboxylate groups from one (1,3-bdc)2− ligand
with coordiantion mode VI (Scheme 3) and arranged in a
staggered ABAB pattern, generating a wavelike 2D framework
(Figure 5b). The 2D netwoks are further linked by Zn4−O15
and Zn4−O16 bonds to give rise to a 3D framework (Figure
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Crystal Growth & Design
Figure 4. (a) Coordination environment of ZnII ions in 4. The hydrogen atoms are omitted for clarity (symmetry codes: A = −x + 1, −y + 1, −z; B =
−0.5 + x, 0.5 − y, −0.5 + z; C = 0.5 − x, −0.5 + y, −0.5 − z). (b) A view of the [Zn2(μ2−OH)(μ2-O2CR)] unit. (c) A perspective view of the 2D
bilayer structure of 4 along the b axis and the 1D loop chain inside it. (d) Schemetic view of the 2D gek1 net: the L− anions and dizinc units are
marked as blue and red, respectively.
5c). To further understand the structure of 5, topological
analysis by reducing complicated structure to simple node-and-
linker net was referred. In accordance with the simplification
principle,38 each pentanuclear zinc cluster can be regarded as a
12-connected node, Zn3 and Zn4 atoms can be defined as 3-
and 4-connected nodes, two kinds of L− anions containing
different pyridyl rings (N1, N3 and N4, and N6) can be
considered as 3- and 4-connected nodes, respectively, while
(1,3-bdc)2− anions act as linkers. Hence, the overall structure of
5 is a self-penetrating 5-nodal (3,3,4,4,12)-connected network
with the point symbol of (4·62)2(42·64)4(43)2(48·634·822·102)
(Figure 5d).
Crystal Structure of [Zn2(L)2(1,4-bdc)]n·nH2O (6). To
further examine the inflence of the auxiliary ligands on the
structure, we used H2(1,4-bdc) instead of H2(1,3-bdc). When
H2(1,4-bdc) was used as the auxiliary ligand, a new 2-fold
interpenetrating 3D coordination polymer was obtained. The
asymmetric unit of 6 contains one Zn(II) cation, one L−, half
(1,4-bdc)2− anions, and one lattice water molecule. As show in
Figure 6a, Zn1 is four-coordinated to two nitrogen atoms (N1,
N3A) of different L− ligands [Zn1−N1=2.043(4) Å and Zn1−
N3A = 2.065(4) Å] and two oxygen atoms (O1A, O3) from a
L− anion and a (1,4-bdc)2− anion, respectively, in turn, forming
a distorted tetrahedral coordination geometry. Apart from the
monodentate carboxylate group, two terminal pyridyl rings are
all coordinated, thus, the L− anion acts as a tridentate-bridging
coordiantion mode V (Scheme 3), linking three Zn1 ions into a
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new {Zn3O2N5C26} 36-membered ring containing a type of
pore with a size of ca. 15.745 × 12.957 Å based on the distances
of Zn1···C8 and Zn1···C6. Then such rings are linked through
the L− anion forming 2D layers (Figure 6b). Finally, the (1,4-
bdc)2− anion adopting the μ2-η1:η1-bridging coordination mode
X (Scheme 3) link the 2D layers giving rise to the formation of
an infinite 3D network, while the L− anions are arranged in a
staggered ABAB pattern (Figure 6c). The networks inter-
penetrate to each other to generate a fascinating 2-fold
interpenetrating network. Topologically, Zn1 ion and L−
anion can be regarded as 4- and 3-connected nodes,
respectively, and complex 6 possesses a 2-nodal (3,4)-
connected INS-net with the point symbol of (63)(65·8) which
is caculated by TOPOS (Figure 6d).
Crystal Structure of [Cd2(L)4]n·nH2O (7). Single-crystal X-
ray crystallography reveals that 7 exhibits a 2D network. The
asymmetric unit of 7 contains one Cd(II) ion, two L− anions,
and half a lattice water molecule. As illustrated in Figure 7a,
Cd1 is six-coordinated by two pairs of chelating oxygen atoms
(O1, O2, O3, and O4) and two nitrogen atoms (N1A and
N4B) from two different L− anions, forming a distorted
octahedral geometry. The O2, O4, N1A, and N4B atoms
comprise the equatorial plane, and the O1 and O3 atoms
occupy axial positions [O1−Cd1−O3 = 146.96(8)°]. The Cd−
O bond lengths are in the range of 2.307(2)−2.4092(19) Å and
Cd−N bond lengths are 2.276(2) and 2.290(2) Å, which are
consistent with corresponding values reported for Cd(II)
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Crystal Growth & Design Article

Figure 5. (a) Coordination environment of Zn(II) ions in 5. The hydrogen atoms are omitted for clarity (symmetry codes: A = +x, +y − 1, +z; B =
−x + 2, −y + 2, −z + 1; C = −x + 2, −y + 1, −z + 1; D = −x + 2, −y, −z + 1; E = +x, +y, +z + 1; F = −x + 1, −y + 1, −z; G = −x + 2, −y + 2, −z; H
= +x + 1, +y − 1, +z). (b) View of the 2D structure and the pentanuclear [Zn5(μ3-OH−)2(COO)4] cluster units in 5. (c) View of the 3D framework
along the b axis. (d) Schemetic view of the 3D topology network: the L− anions are marked as green and light blue. The pentanuclear Zn units are
marked as red. The blue and yellow balls represent the Zn4 and Zn3 ions, respectively. And the perspective view of the ring links between 8-
membered shortest rings inside the net.

Figure 6. (a) Coordination environment of ZnII ion in 6. The hydrogen atoms are omitted for clarity (Symmetry codes: A = −0.5 + x, −y, −0.5 + z).
(b) View of the 2D layer in 6. (c) A perspective view of the 3D net of 6 along the a axis. (d) Schemetic view of the 2-fold interpenetrating network:
the green spheres represent ZnII ions.

1636 dx.doi.org/10.1021/cg4016977 | Cryst. Growth Des. 2014, 14, 1629−1641

Crystal Growth & Design
Figure 7. (a) Coordination environment of Cd(II) ion in 7. The hydrogen atoms are omitted for clarity. (symmetry codes: A = 1+x, 1+y, z; B = x,
−1+y, z). (b) View of the 1D zigger chain of 7. (c) View of the 2D layer in 7.
compounds.41 The three pyridyl rings of the L− ligand are
nonplanar; each terminal pyridyl group is twisted with respect
to the central one, and the dihedral angles between the central
and terminal pyridyl rings are 16.22° (N1 pyridyl ring) and
11.42° (N3 pyridyl ring), respectively. Each L− anion adopting
μ2-η1:η2 (Scheme 3, mode II) link two Cd(II) ions to form a
1D zigger chain (Figure 7b). The adjacent 1D chains are
parallel to each other and are further connected by the nitrogen
atom and carboxylate group of L− anions to generate a 2D layer
(Figure 7c).
Crystal Structure of [Cd3(L)2(1,3-bdc)2]n·nH2O (8). The
single-crystal X-ray structural analysis indicates that complex 8
displays a 3D network built up by linear Cd3(COO)6 trinuclear
clusters. The asymmetric unit of 8 contains one and a half
Cd(II) ions, one L− anion, one (1,3-bdc)2− anion, and a half
lattice water molecule. As shown in Figure 8a, the Cd1 is hexa-
coordinated by four oxygen atoms (O1, O3, O4, and O5C)
from two (1,3-bdc)2− anions and one L− anion and two
nitrogen atoms (N1A, N3B) from two L− anions. The
coordination geometry of Cd1 can be described as a slightly
distorted octahedron. The O3, O4, O5C, and N1A atoms
comprise the equatorial plane, and the O1 and N3B atoms
occupy the apical positions. The Cd1−N bond lengths are
2.348(6) Å and 2.365(5) Å, respectively. The Cd1−O distances
fall in the range of 2.240(5)−2.697(5) Å. Cd2 adopts an
octahedral [O6] coordination environment and is coordinated
by six oxygen atoms (O2, O2D, O3, O3D, O6C, and O6E)
from two L− anions and four (1,3-bdc)2− anions, in which O6C
and O6E atoms occupy the axial positions [O6C−Cd2−O6E =
180.0(3)°]. The Cd2−O distances are in the range of 2.251(5)-
2.290(4) Å. The (1,3-bdc)2− anion acts as a μ4-bridge to link
one Cd2 and two Cd1 ions, in which two carboxylate groups
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Article
adopt μ3-η1:η2:η1 and μ2-η1:η1 coordination fashions, respec-
tively. Cd1, symmetry-related Cd1A (−x, 2 − y, −z) and Cd2
are bridged by six carboxylate groups to form a linear
Cd3(COO)6 trinuclear cluster (Figure S1 of the Supporting
Information). Each trimer is connected to two others via two
pairs of L− anions that show a μ4-η1:η1:η1:η1 coordination mode
(Scheme 3, mode III), resulting in the formation of a 1D chain
(Figure S2 of the Supporting Information). Then these chains
are further linked by the nitrogen atom and carboxylate group
of L− anions to give rise to a 2D layer (Figure 8b). Finally, the
two-dimensional layers are extended into a 3D network
through chelating-bridging (1,3-bdc)2− anions (Figure 8c).
To get deep insight into the structure of 8, the topological
analysis was carried out. Both the L− and (1,3-bdc)2− anions
can be regarded as a 4-connected node. Cd1 ion is attached to
four L− anions and one (1,3-bdc)2− anion, which is assigned to
a 5-connected node, and the Cd2 ion is coordinated to two L−
anions and four (1,3-bdc)2− anions and thus can be considered
as a 6-connected node. On the basis of the simplification
principle,38 complex 8 possesses a 4-nodal (4,4,5,6)-connected
network with the point symbol of (42.63.8)2(43.63)2(44.64.82)2-
(48.66.8) (Figure 8d).
Comparison of Synthetic Conditions and Structures.
The syntheses were summarized in Scheme 2. Hydro(solvo)-
thermal synthesis has proven to be a powerful method in the
preparation of coordination polymers. Compounds 1 and 2
were synthesized by using different metal salts without the
auxiliary ligand under the same hydrothermal synthesis
conditions. When ZnCl2 was used instead of Zn(Ac)2·2H2O,
compound 2 was obtained. Although compounds 1 and 2 both
show 2D layer frameworks, they possesse different structures
and luminescent properties due to the coordination of the
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Crystal Growth & Design
Figure 8. (a) Coordination environment of CdII ions in 8. The hydrogen atoms are omitted for clarity (symmetry codes: A = −x, 2 − y, 1 − z; B =
−0.5 − x, 0.5 + y, 0.5 − z; C = x, −1 + y, z; D = −x, 2 − y, −z; E = −x, 3 − y, −z). (b) View of the 2D structure. (c) View of the 3D framework
along the c axis. (d) Schemetic view of the 3D topology network: the L− anion, (1,3-bdc)2− anion, and Cd ion are marked as orange, blue, and green,
respectively.
chloride atom in compound 1. There is no denying that
counteranions are significant in determing the structure of
complexes. Anions are able to assist the construction of
supramolecular architectures and self-assemblies.42 Apart from
that, counteranions do not contribute to the process of
construction; they might balance the electric charge of the
structure and in turn affect it. Compound 1 was obtained at pH
= 4. When the reaction system is weakly acidic, Cl− is easy to
coordinate. On the contrary, acetate is protonized, so it is
difficult for it to participate in coordination. When H2(1,3-bdc)
was introduced into the reaction system, compound 3 was
obtained with a 2D layer structure containing paddle-wheel
units. When we use Zn(Ac)2·2H2O instead of Zn(NO3)2·6H2O
and adjust pH values, compounds 4 and 5 were generated.
Compound 4 is a 2D layer structure, while compound 5
displays a 3D network containing pentanuclear Zn(II) clusters.
Different pH values in reaction systems lead to various
coordination fashions of the ligands and result in distinct
ultimate structures. Afterward, in order to investigate the effects
of the steric hindrance effect of the substituted group in the
auxiliary ligand on the self-assembly of supramolecules and
coordination polymers, H2(1,4-bdc) was employed in place of
H2(1,3-bdc). As a result, compound 6 was obtained. The nature
(coordination ability, mode, and donor character) of the
auxiliary ligands is the underlying reason behind the different
structures of several complexes.43−45 Belonging to the same
kind of bridging ligands in a certain sense, the figuration of
H2(1,3-bdc) and H2(1,4-bdc) are quite similar. Nevertheless, 6
shows a 2-fold interpenetrating 3D network, while 4 possesses a
2D bilayer structure. The difference of the structures can be
1638
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attributed to the different orientations of binding sites in
auxiliary ligands. In addition, it is noteworthy that the central
metal cations also have significant inflence on the final
structures. When CdCl2·2.5H2O was introduced into the
reaction system, compounds 7 and 8 were obtained.
Compound 7 is a 2D layer structure, while compound 8
displays new 3D network built up by linear Cd3(COO)6
trinuclear clusters. Because the radius of Cd(II) is longer
than that of Zn(II), they may have different coordination
numbers and geometry, which lead to different structures.
Furthermore, we also attempted other second ligands, such as
oxalic acid, malic acid, and 1,3,5-benzenetricarboxylic acid
instead of H2(1,3-bdc), but only obtained compound 7 not
other new structures. These results indicate that reaction
conditions such as pH value, counteranion, metal cation, and
auxiliary ligand are significant in determining the ultimate
structures of the compounds. Meanwhile, we also find that the
L− ligand and auxiliary ligand can afford relatively various
coordination modes to meet the coordination requirements of
the center metal ions.
Luminescent Properties. Taking into account the
excellent luminescent properties of the terpyridyl species and
d10 metal ions compounds,46 the luminescence of the free HL
ligand and 1−8 were investigated at room temperature.
Unfortunately, compound 1 exhibits very weak emission. As
shown in Figure 9, the free ligand exhibits one weak emission
band at 384 nm upon excitation at 306 nm. Upon excitation at
310 nm, intense emission is observed at 381, 387, 380, and 392
nm for 2, 3, 4, and 6, respectively, which may be assigned to the
intraligand transition of the ligand. Notably, compound 5
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Crystal Growth & Design
Figure 9. The solid state emission spectra of the HL and 2−8 at room
temperature.
displays a weaker emission band at 389 nm, which can also be
attributed to the intraligand transition of the ligand. Meanwhile,
the weakened emission peak in 5 may be the result from the
weakened conjugacy after coordination. Additionally, com-
pounds 7 and 8 show emssion at 409 nm for 7 and 397 nm for
8, which may also be assigned to the intraligand transition of
the ligand. The enhancement of luminescence intensity for
compounds 2−8 compared to the free ligand is perhaps a result
of the metal−ligand coordination, which effectively increases
the rigidity of the ligand and reduces the nonradiative decay of
the intraligand (π−π*) excited state.47,48 Furthermore, the
emission decay lifetimes of compounds 2−8 were measured
and the curves (Figure S3−S9 of the Supporting Information)
are best fitted by biexponentials in the solid state.49−51 The
emission decay lifetimes of compounds 2−8 are summarized in
Table 2. The nanosecond range of lifetime in the solid state at
room temperature indicates that the emission is fluorescent in
nature.
Table 2. Emission Lifetimes of Compounds 2−8
compound τ1 (ns) τ2 (ns) χ2
2 1.26 5.42 1.159
3 1.61 5.46 1.091
4 1.98 6.68 1.077
5 1.50 5.26 0.944
6 1.89 6.54 1.066
7 1.32 3.95 1.428
8 1.50 3.60 1.065
PXRD and Thermogravimetric Analysis. Powder X-ray
diffraction experiments were carried out for the primitive
samples of complexes 1−8. The observed powder X-ray
diffraction (PXRD) patterns are in good agreement with
those simulated on the basis of the single-crystal X-ray
diffraction data (Figure S10 of the Supporting Information)
and indicated the phase purity of the as-synthesized products.
To examine thermal stability of these frameworks, thermal
gravimetric analysis (TGA) measurements were carried out.
Compound 1 was stable to 450 °C and then began to
decompose upon further heating. The first continuous weight
loss of 77.81% happened in the temperature range of 450−595
°C, which can be attributed to the loss of L− ligands (calcd
77.75%). The second weight loss of 7.79% between 690 and
800 °C was assigned to the release of chloride anions (calcd
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7.82%). The remaining weight is assigned to zinc oxide (obsd
17.94%, calcd 17.96%). The TG curve of 2 shows an initial
weight loss of 2.42% below 200 °C, corresponding to the
removal of lattice water molecules (calcd 2.36%). Then the
framework is stable to nearly 400 °C, where a continuous
weight loss of 89.71% was observed from 400 to 610 °C, which
can be ascribed to the decomposition of L− ligands (calcd
89.65%). The residue product of 10.31% is zinc oxide (calcd
10.35%). Compound 3 was stable to 400 °C and then began to
decompose upon further heating. The weight loss of 16.45% in
the temperature range of 400−495 °C is attributed to the
removal of (1,3-bdc)2− ligands (calcd 16.42%). The weight loss
of 70.46% from 580 to 790 °C can be ascribed to the release of
L− ligands (calcd 70.50%). The residue product of 16.24%
cooresponds to zinc oxide (calcd 16.28%). Compound 4 shows
an initial weight loss of 1.36% below 300 °C, corresponding to
the removal lattice water molecules (calcd 1.34%). The second
step weight loss of 23.60% between 290 and 500 °C indicated
the decomposition of (1,3-bdc)2− ligands (calcd 24.41%), and
the weight loss of 51.68% between 500 and 790 °C attributed
to the loss of L− ligands (calcd 52.42%). The remaining weight
may be assigned to the formation of zinc oxide (obsd 23.80%,
calcd 24.21%). Compound 5 released its lattice water molecules
below 210 °C (obsd 1.78%, calcd 1.74%), and then the
compound was stable up to 400 °C and was followed by a two-
step weight loss in the temperature range of 400−900 °C,
which were assigned to the decomposition of (1,3-bdc)2− and
L− ligands (obsd 31.80%, calcd 31.76%; obsd 45.43%, calcd
45.46%), respectively. The remaining weight of 23.59% is zinc
oxide (calcd 23.62%). With regard to 6, the first weight loss of
1.79% below 100 °C is consistent with the removal of its lattice
water molecules (calcd 1.77%). After this process, a weight loss
of 16.19% from 200 to 390 °C was observed, which can be due
to the release of (1,3-bdc)2− ligands (calcd 16.13%). The last
weight loss of 69.33% in the temperature range of 480−700 °C
can be attributed to the decomposition of L− ligands (calcd
69.25%). The final residual weight is likely assigned to zinc
oxide (obsd 16.03%, calcd 16.00%). Compound 7 first loses its
lattice water molecule below 200 °C (obsd 1.12%, calcd
1.09%), and then the compound was stable up to 480 °C and
followed by a continuous weight loss of 85.45% in the
temperature range of 480−700 °C (calcd 85.41%), which were
attributed to the decomposition of L− ligands. The residue
product of 15.61% cooresponds to cadmium oxide (calcd
15.56%). For compound 8, the first weight loss of 1.34%
happened below 210 °C corresponds to the removal of lattice
water molecules (calcd 1.31%). The second step weight loss of
24.02% between 290 and 500 °C indicated the decomposition
of (1,3-bdc)2− ligands (calcd 23.96%), and the weight loss of
51.48% between 500 and 790 °C attributed to the loss of L−
ligands (calcd 51.43%). The remaining weight is assigned to the
formation of cadmium oxide (obsd 28.16%, calcd 28.12%).
TGA results of 1−8 indicate they all possess great thermal
stability (Figure S11 of the Supporting Information, shows the
TG curves for 1−8).
■
CONCLUSION
In summary, eight new coordination polymers with diverse
structures were successfully constructed from the 4′-(2-
carboxyphenyl)-4,2′:6′,4″-terpyridine ligand under hydrother-
mal conditions. The compounds 1−8 display intriguing 2D and
3D structures. The result of the present work demonstrates that
rational adjustment of the second ligand, the pH value, and the
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Crystal Growth & Design
counteranion are good methods to further design metal−
organic compounds with new structures and properties.
Moreover, the thermal stabilities and photoluminenscence
properties were also studied. The results indicate that
compounds 2−8 possess excellent fluorescence properties
and high thermostability, which are likely to be potential
luminescent materials.
■
ASSOCIATED CONTENT
*
S Supporting Information
X-ray crystallographic files in CIF format, selected bond
distances, and bond angles for 1−8, the coordination modes
of (1,3-bdc)2− anion and trinuclear CdII subunit of 8, the view
of 1D loop chain inside 8, the fitted decay curve of 2−8, PXRD
patterns, and thermal analyses. This material is available free of
charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: chemhu1@nwu.edu.cn.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (Grants 20873098 and 21173164).
■
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