Structural characterization of three semi-rigid tetracarboxylate-containing transition-metal coordination polymers

Article abstract of DOI:10.1016/j.poly.2016.05.054

Under hydro(solvo)thermal conditions, the reactions between transition-metal salts and tetracarboxylic acid molecules, with the assistance of organic base molecules, created three new coordination polymers, namely [H₂(bpp)]₂[Zn₂(sph)₂]·H₂O (sph = 4,4′-sulfonediphthalate, bpp = 1,3-bis(piperidyl)propane) 1, [H₂(bpp)]₂[Ni₂(oph)₂(H₂O)₂]·2H₂O (oph = 4,4′-oxydiphthalate) 2 and [H₂(bpe)]₂[Ni(Hfph)₂(bpe)] (bpe = 1,2-bis(pyridyl)ethylene; fph = 4,4′-(hexafluoroisopropylidene)diphthalate) 3. X-ray single-crystal diffraction analysis reveals that (i) in 1, the diprotonated bpp molecule acts as a templating agent. The quadruple-bridged sph molecules propagate the tetrahedral Zn²⁺ ions into a 2-D layer network in 1, where two types of circle loops are found; (ii) in 2, the bpp molecule is also diprotonated. The triple-bridged oph molecules extend the octahedrally coordinated Ni²⁺ ions into a 2-D layer network, in which a carboxylate-bridged Ni²⁺ chain is observed; (iii) in 3, the non-protonated bpe molecules link the Ni²⁺ ions into a 1-D linear chain. The diprotonated bpe molecule acts as the countercation, while the fph molecule serves as the chelating ligand, existing in the form of Hfph^3-; and (iv) the 2-D layers for 1 and 2 can both be simplified as a (4,4) net. The photoluminescence analysis reveals that 1 emits blue light with a maximum at 415 nm upon excitation at 355 nm. A magnetic property investigation indicates that antiferromagnetic interactions exist between the Ni²⁺ ions in 2.

Full text of DOI:10.1016/j.poly.2016.05.054

Polyhedron 117 (2016) 126–132
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Structural characterization of three semi-rigid tetracarboxylate-
containing transition-metal coordination polymers
⇑
⇑
Jing-Jing Huang, Jie-Hui Yu , Ji-Qing Xu
College of Chemistry, Jilin University, Jiefang Road 2519, Changchun, Jilin 130012, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Under hydro(solvo)thermal conditions, the reactions between transition-metal salts and tetracarboxylic
acid molecules, with the assistance of organic base molecules, created three new coordination polymers,
namely [H2(bpp)]2[Zn2(sph)2]ꢀH2O (sph = 4,40-sulfonediphthalate, bpp = 1,3-bis(piperidyl)propane) 1,
Received 23 March 2016
Accepted 18 May 2016
Available online 31 May 2016
[H2(bpp)]2[Ni2(oph)2(H2O)2]ꢀ2H2O (oph = 4,40-oxydiphthalate)
2
and [H2(bpe)]2[Ni(Hfph)2(bpe)]
(bpe = 1,2-bis(pyridyl)ethylene; fph = 4,40-(hexafluoroisopropylidene)diphthalate) 3. X-ray single-crystal
diffraction analysis reveals that (i) in 1, the diprotonated bpp molecule acts as a templating agent. The
quadruple-bridged sph molecules propagate the tetrahedral Zn2+ ions into a 2-D layer network in 1,
where two types of circle loops are found; (ii) in 2, the bpp molecule is also diprotonated. The triple-
bridged oph molecules extend the octahedrally coordinated Ni2+ ions into a 2-D layer network, in which
a carboxylate-bridged Ni2+ chain is observed; (iii) in 3, the non-protonated bpe molecules link the Ni2+
ions into a 1-D linear chain. The diprotonated bpe molecule acts as the countercation, while the fph mole-
cule serves as the chelating ligand, existing in the form of Hfph3ꢁ; and (iv) the 2-D layers for 1 and 2 can
both be simplified as a (4,4) net. The photoluminescence analysis reveals that 1 emits blue light with a
maximum at 415 nm upon excitation at 355 nm. A magnetic property investigation indicates that anti-
ferromagnetic interactions exist between the Ni2+ ions in 2.
Keywords:
Semi-rigidity
Tetracarboxylate
Coordination polymers
Photoluminescence
Magnetic property
Ó 2016 Elsevier Ltd. All rights reserved.
1. Introduction
location, the multicarboxylate molecule directly affects the result-
ing network formation.
Over the past fifty years, metal-multicarboxylate coordination
polymer (CP) chemistry achieved rapid development [1–5].
Metal-multicarboxylate CPs not only possess the rich structures
[6–10], many interesting physical properties have also been inves-
tigated [11–20]. For example, (i) porous metal-multicarboxylate
CPs can selectively adsorb gases, in particular H2 (for energy stor-
age) and CO2 (for purification of the environment) [21–25]; (ii)
Zn2+/Cd2+/Ln3+-multicarboxylate CPs can emit light. Based on this
property, some metal-multicarboxylate CPs have been developed
into molecular devises, such as chemosensors [26–30]; and (iii)
since the carboxylate groups can link metal ions to form various
clusters or chains, the metal-multicarboxylate CPs exhibit excel-
lent magnetic properties [31–35]. In the construction of the
metal-multicarboxylate network, the multicarboxylate molecule
plays a key role. By varying the size, charge, configuration, rigid-
ity/flexibility, substituent, carboxylate number and the carboxylate
Recently, a class of semi-rigid multicarboxylic acid molecules
has attracted the attention of researchers [36,37,32,38–44]. They
generally consist of several benzene ring moieties. Two neighbor-
ing benzene rings are connected by a non-metallic atom or a group.
The so-called semi-rigidity means that the tetrahedron for the cen-
tric non-metallic atom can be slightly distorted, and the two adja-
cent benzene rings can appropriately rotate around the centric
atom. In the past, we have employed several semi-rigid multicar-
boxylic acid molecules to construct some CPs [45–49]. In this arti-
cle, the semi-rigid tetracarboxylic acid molecules H4sph
(sph = 4,40-sulfonediphthalate), H4oph (oph = 4,40-oxydiphthalate)
and H4fph (fph = 4,40-(hexafluoroisopropylidene)diphthalate) were
selected, and with the assistance of organic base molecules, three
new transition-metal CPs, [H2(bpp)]2[Zn2(sph)2]ꢀH2O (bpp = 1,3-
bis(piperidyl)propane) 1, [H2(bpp)]2[Ni2(oph)2(H2O)2]ꢀ2H2O 2 and
[H2(bpe)]2[Ni(Hfph)2(bpe)] (bpe = 1,2-bis(pyridyl)ethylene) 3,
were obtained under hydro(solvo)thermal conditions. Here we will
report their structural characterization.
⇑
Corresponding authors. Tel.: +86 431 88499132; fax: +86 431 85168624.
E-mail addresses: jhyu@jlu.edu.cn (J.-H. Yu), xjq@mail.jlu.edu.cn (J.-Q. Xu).
http://dx.doi.org/10.1016/j.poly.2016.05.054
0277-5387/Ó 2016 Elsevier Ltd. All rights reserved.

J.-J. Huang et al. / Polyhedron 117 (2016) 126–132
127
Table 1
2. Experimental
Crystal data of the title compounds.
2.1. Materials and physical measurements
1
2
3
Formula
M
T (K)
Crystal system
Space group
a (Å)
C
58H62N4O21S2Zn2 C58H76N4O22Ni2 C74H48N6O16F12Ni
All chemicals were of reagent grade quality, obtained from com-
mercial sources without further purification. Elemental analysis (C,
H and N) was performed on a Perkin–Elmer 2400LS II elemental
analyzer. Infrared (IR) spectra were recorded on a Perkin Elmer
Spectrum 1 spectrophotometer in the 4000–400 cmꢁ1 region using
a powdered sample on a KBr plate. Powder X-ray diffraction (XRD)
data were collected on a Rigaku/max-2550 diffractometer with Cu
1346.04
293(2)
monoclinic
P21
1298.65
293(2)
1563.87
293(2)
triclinic
P1
triclinic
P1
ꢀ
ꢀ
9.8817(6)
24.8194(14)
12.3018(8)
90
97.504(4)
90
2991.3(3)
2
1.494
10.0855(5)
10.7409(5)
13.5815(8)
98.241(3)
91.246(3)
94.517(3)
1450.72(13)
1
9.2544(13)
13.5680(17)
13.938(2)
78.982(9)
89.070(10)
79.747(9)
1690.1(4)
1
b (Å)
c (Å)
a
(°)
b (°)
Ka radiation (k = 1.5418 Å). Thermogravimetric (TG) behavior was
c
(°)
investigated on a Perkin–Elmer TGA-7 instrument with a heating
rate of 10 °C minꢁ1 in air. Fluorescence spectra were obtained on
a LS 55 florescence/phosphorescence spectrophotometer at room
temperature.
V (Å3)
Z
Dc (g cmꢁ3
)
1.486
1.536
l
(mmꢁ1
)
0.953
16966
0.734
0.397
Reflections
collected
Unique
reflections
Rint
8226
9561
9953
5091
5962
2.2. Synthesis of the title compounds
0.0336
1.043
0.0248
1.058
0.0368
1.079
2.2.1. Synthesis of 1
Goodness-of-fit
Colorless columnar crystals of 1 were obtained from the simple
solvothermal self-assembly of Zn(OAc)2ꢀ2H2O (0.2 mmol, 44 mg),
4,40-sulfonephthalic dianhydride (0.1 mmol, 36 mg) and bpp
(0.1 mmol, 21 mg) in a 10 mL H2O and CH3OH solution (volume
ratio = 4:1; pH = 7 neutralized by triethylamine) at 140 °C for
3 days. Yield: ca. 20% based on Zn(II). Anal. Calc. for C58H70N4O21S2-
Zn2 1: C, 51.40; H, 5.21; N, 4.14. Found: C, 50.73; H, 5.09; N, 4.12%.
IR (cmꢁ1): 2949 m, 2846 m, 1627 s, 1573 s, 1471 m, 1482 w, 1388
s, 1316 s, 1160 m, 1077 m, 903 m, 840 s, 675 s, 622 s, 498 m (see
Fig. S1).
(GOF) on F2
R1, I > 2
r
(I)
0.0349
0.0961
0.0369
0.1071
0.0982
0.2931
wR2, all data
tures were then refined on F2 using SHELXL-97 [50]. The crystal data
of 1–3 are summarized in Table 1.
3. Results and discussion
3.1. Synthetic analysis
2.2.2. Synthesis of 2
All of the compounds were obtained under hydro(solvo)thermal
conditions. In the reactions, the pH level of the reactive system
plays a crucial role: (i) it directly influences the crystal growth.
The optimal pH conditions for the crystal growth is 7 for 1, 7 for
2, and 5 for 3; (ii) it directly influences the deprotonation reaction
of the tetracarboxylic acid molecule. At pH = 7, the tetracarboxylic
acid molecule completely deprotonates, as observed in 1 and 2,
while at pH = 5, it only partly deprotonates, as observed in 3; and
(iii) it directly influences the protonation reaction of the organic
base molecule. As found in 1–3, the organic base molecule has a
potential to be protonated at pH 6 7, but obviously, the bpp mole-
cule is more easily protonated than the bpe molecule, because at
pH = 7, the protonation reaction for the bpp molecule has occurred,
while at pH = 5, the partial bpe molecule still exists in the form of
the neutral molecule.
Green columnar crystals of 2 were obtained from the simple
hydrothermal self-assembly of Ni(NO3)2ꢀ6H2O (0.2 mmol, 58 mg),
4,40-oxydiphthalic anhydride (0.1 mmol, 44 mg) and bpp
(0.1 mmol, 21 mg) in a 10 mL aqueous solution (pH = 7 neutralized
by dilute NaOH) at 120 °C for 3 days. Yield: ca. 17% based on Ni(II).
Anal. Calc. for C58H76N4Ni2O22 2: C, 53.64; H, 5.90; N, 4.31. Found:
C, 54.03; H, 5.88; N, 4.30%. IR (cmꢁ1): 2933 w, 2852 w, 1584 s, 1559
s, 1398 s, 1253 m, 1222 m, 1155 w, 963 m, 918 w, 886 w, 961 w,
821 s, 622 w, 565 w, 520 w (see Fig. S1).
2.2.3. Synthesis of 3
Green columnar crystals of 3 were obtained from the simple
hydrothermal self-assembly of Ni(NO3)2ꢀ6H2O (0.2 mmol, 58 mg),
4,40-(hexafluoroisopropylidene)diphthalic anhydride (0.1 mmol,
44 mg) and bpe (0.15 mmol, 27 mg) in a 10 mL aqueous solution
(pH = 5 adjusted by dilute NaOH) at 120 °C for 3 days. Yield: ca.
15% based on Ni(II). Anal. Calc. for C74H48F12N6NiO16 3: C, 56.83;
H, 3.09; N, 5.34. Found: C, 56.92; H, 2.83; N, 5.37%. IR (cmꢁ1):
1714 s, 1606 s, 1579 s, 1502 w, 1420 s, 1259 s, 1206 w, 1181 m,
1161 w, 1067 w, 963 m, 902 w, 835 s, 716 w, 612 w, 551 w (see
Fig. S1).
3.2. Structural description
3.2.1. Structural description of 1
1 is a sph-bridged 2-D layered Zn2+ CP. Bpp should exist in the
diprotonated form in order to balance the systematic charge. 1
crystallizes in the space group P21 and the asymmetric unit is
found to be composed of two types of Zn2+ ions (Zn1 and Zn2),
two types of sph molecules (sph I, sph II), two types of H2(bpp)2+
molecule (bpp I, bpp II) and one lattice water molecule (Ow1).
Since the two types of Zn2+ ions have the same coordination envi-
ronment and the two types of sph molecules adopt the same coor-
dination mode, only Zn1 and sph I, as representatives, are
described. As shown in Fig. 1c, the Zn1 ion is in a tetrahedral site,
completed by four carboxylate O atoms (O2, O8a, O10a, O12).
The Zn1–O bond length range is 1.930(2)–2.007(2) Å. Fig. 1d shows
the coordination environment around the Zn2 ion. The sph I ligand
2.3. X-ray crystallography
The data were collected with Mo K
a radiation (k = 0.71073 Å)
on a Siemens SMART CCD diffractometer. With the SHELXTL program,
all of the structures were solved using direct methods [50]. The
non-hydrogen atoms were assigned anisotropic displacement
parameters in the refinement, and the other hydrogen atoms were
treated using a riding model. The H atoms on the water molecules
in 1 and 2, and on the O6 atom in 3 were not located. The H atoms
on the bpp molecule in 1 and 2 were not located, either. The struc-
adopts the g1 g0 g1 g1 g1 g0 g1 g0
: : : : : : : :l3 coordination mode (see

128
J.-J. Huang et al. / Polyhedron 117 (2016) 126–132
(a)
(c)
c
b
(d)
(b)
(e)
Fig. 1. 2-D layer network (a), coordination mode of sph (b), coordination environments around Zn1 (c) and Zn2 (d), and projection plot in the (001) direction (e) in 1 (a:
ꢁx ꢁ 2, y + 1/2, ꢁz ꢁ 2; b: ꢁx ꢁ 3, y ꢁ 1/2, ꢁz ꢁ 3).
Fig. 1b). The triple-bridged sph molecules link the tetrahedral Zn2+
centers into a 2-D layer network in 1 (see Fig. 1a). In the layer, two
types of circle loops (loops A and B) are observed. Loop A is com-
prised of four Zn2+ centers and four sph molecules, linked through
an alternate arrangement, while an alternate arrangement of two
Zn2+ centers and two phthalate moieties forms loop B. Based on
the topological method, the loop B can be viewed as a 4-connected
node, while the sph molecule serves as a linker. So the 2-D layer of
1 has a simple (4,4)-topology. The shortest Znꢀ ꢀ ꢀZn separation in
the layer is Zn1ꢀ ꢀ ꢀZn2 = 5.617 Å. As displayed in Fig. 1e, the bpp
molecule serves as a templating agent, occupying the space
between the 2-D layers. The bpp II molecules act as bridges,
tance of 2.1055(17) Å is slightly longer. Oph adopts a tetra-bridged
coordination mode (see Fig. 2d). Each carboxylate group coordi-
nates with one O atom (O1, O3, O6, O7) to one Ni2+ ion. Meanwhile,
the O8 atom also participates in the coordination, sharing one Ni2+
center (Ni2) with O6. The
l4-mode oph molecules link two types
of octahedral Ni(II) centers into a 2-D layer network in 2. Interest-
ingly, a carboxylate-bridged Ni2+ chain is observed within the
layer, in which this carboxylate group adopts a syn-anti mode.
Based on the topological viewpoint, the Ni2+ center can be regarded
as a 4-conneted node, and the oph molecules acts as linkers. So the
2-D layer of 2 also possess a simple (4,4) topology. The shortest
Niꢀ ꢀ ꢀNi contact distance in the layer is Ni1ꢀ ꢀ ꢀNi2b = 5.043 Å. The
H2(bpp)2+ molecules occupy the space between the 2-D layers
(see Fig. 2e). Via N–Hꢀ ꢀ ꢀO interactions (N1ꢀ ꢀ ꢀO4 = 2.690 Å,
N2ꢀ ꢀ ꢀO5 g = 2.735 Å), the H2bpp2+ molecules propagate the 2-D
Ni-oph layers into a 3-D supramolecular network (see Fig. S3).
extending the Zn-sph layers into
a
3-D supramolecular
network via interactions
N–Hꢀ ꢀ ꢀO
(N3ꢀ ꢀ ꢀO17c = 2.796 Å,
N4ꢀ ꢀ ꢀO10d = 2.841 Å), while two N atoms from bpp I form hydro-
gen bonds to the carboxylate O atoms from an identical Zn-sph
layer (N1ꢀ ꢀ ꢀO20e = 2.750 Å, N2ꢀ ꢀ ꢀO13f = 2.738 Å, as shown in
Fig. S2.
3.2.3. Structural description of 3
3 is a bpe-extended 1-D chained Ni2+ CP. It crystallizes in the
ꢀ
3.2.2. Structural description of 2
space group P1 and the asymmetric unit is found to be composed
2 is an oph-propagated 2-D layered Ni2+ CP. Bpp exists in the
of a half Ni2+ ion (Ni1), one fph molecule and two types of bpe
molecules (bpe I and bpe II). Note, only a half bpe II molecule
appears in the asymmetric unit of 3. Fig. 3a plots the 1-D chain
structure of 3. Unprecedentedly, the fph molecule does not act as
a bridging liand. It just chelates to a Ni2+ center with two O donors
(O1, O3; Ni1–O1 = 2.111(5) Å, Ni1–O3 = 2.051(5) Å). Bpe II acts as a
bridge, linking the octahedral Ni2+ centers into a 1-D linear chain
(\Niꢀ ꢀ ꢀNiꢀ ꢀ ꢀNi = 179°), running down the c-axial direction. The
Ni1–N3 distance is 2.100(5) Å. Although the O7 and O8 atoms do
not interact with the Ni2+ centers, this carboxylate group should
be deprotonated, which is confirmed by the two equivalent C–O
distances (C28–O7 = 1.216(11) Å, C28–O8 = 1.219(12) Å). The
C27–O5 distance (1.242(12) Å) is obviously shorter than that of
ꢀ
diprotonated form in 2. 2 crystallizes in the space group P1 and
the asymmetric unit is found to be composed of two types of
Ni2+ ions (Ni1, Ni2; occupancy ratio: 0.5 for each), one oph mole-
cule, one diprotonated bpp molecule, one coordinate water mole-
cule (Ow1) and one lattice water molecule (Ow2). Templating by
H2(bpp)2+, 2 exhibits a 2-D layer structure, as shown in Fig. 2a.
Two crystallographically independent Ni2+ centers are both in
octahedral sites (see Fig. 2b and c). Ni1 is coordinate by four car-
boxylate O atoms (O1, O1a, O7b, O7c) and two water molecules
(Ow1, Ow1a), while Ni2 is surrounded by six carboxylate O atoms
(O3d, O3e, O6, O6f, O8, O8f). The Ni–Ocarboxylate distances span a
narrow range from 1.9978(17) to 2.0851(16) Å. The Ni–Ow dis-

J.-J. Huang et al. / Polyhedron 117 (2016) 126–132
129
(b)
(a)
(c)
c
b
(e)
(d)
Fig. 2. 2-D layer network (a), coordination environments around Ni1 (b) and Ni2 (c), coordination mode of oph (d) and projection plot in the (100) direction (e) in 2 (a: ꢁx + 1,
ꢁy, ꢁz + 2; b: x, y, z + 1; c: ꢁx + 1, ꢁy, ꢁz + 1; d: ꢁx, ꢁy, ꢁz + 1; e: x, y, z ꢁ 1; f: ꢁx, ꢁy, ꢁz).
C27–O6 (1.295(14) Å), indicating that this carboxylate group does
not deprotonate. So in 3, fph has a ꢁ3 oxidation state and should
be labeled as H(fph)3ꢁ. The bpe I molecule should be diprotonated,
in order to balance the system charge. As shown in Fig. 3b, both
bpe I N atoms form hydrogen bonds to the adjacent carboxylate
O atoms (N1ꢀ ꢀ ꢀO2b = 2.546 Å, N2ꢀ ꢀ ꢀO7c = 2.701 Å). Via the N–
Hꢀ ꢀ ꢀO interactions, the 1-D chains are propagated into a 2-D
supramolecular sheet network. Since each Ni2+ center is sur-
rounded by two fph molecules, the 2-D supramolecular sheet pos-
sesses a certain thickness. The octahedral Ni1 center is coordinated
by four carboxylate O atoms (O1, O3, O1a, O3a) and two bpe N
atoms (N3, N3a). No weak interactions are found between the 2-
D supramolecular layers (see Fig. S4).
character of the molecules cpph and bcbob. While for the title
tetracarboxylate molecules, it should be difficult to form a 3-D net-
work with such large pores.
3.4. Characterization
3.4.1. TG analysis of 1–3
The TG behaviors of 1–3 were investigated. Fig. 4 gives the tem-
perature versus weight-loss curves. 1 underwent four steps of
weight loss. Since the water content in 1 is rather low (Calcd:
1.34%), the first step of weight loss for 1 was not obvious (Found:
ca. 1.50%). From ca. 310 °C, 1 underwent three-steps of continuous
weigh loss, corresponding to the removal of the organic bpp and
sph molecules. The final remaining residue was proven to be ZnO
(Calcd: 12.09%; Found: ca. 13.23%). 2 underwent three steps of
weight loss. The first step was a minor weight loss of ca. 4.50%,
which should be attributed to sublimation of the water molecule
in 2 (Calcd: 5.50%). From ca. 310 °C, the second step of weight loss
for 2 started. In the temperature range of 310–455 °C, 2 underwent
two-steps of continuous weigh loss, corresponding to the decom-
position of the organic bpp and oph molecules. The final residue
is NiO (Calcd: 11.50%; Found: ca. 11.50%). 3 was thermally stable
up to ca. 270 °C. At about ca. 490 °C, the decomposition of the
organic compositions in 3 completed; synchronously, Ni2+ com-
bined with O2 to generate NiO (Calcd: 4.78%; Found: ca. 4.89%).
3.3. Structural discussion
In 1–3, the tetracarboxylate molecules exhibit a semi-rigid
character. On the one hand, the tetrahedral configurations for the
centric non-metal atoms suffer from severe deformation: 106.55
(16)–120.0(2)° in 1, 117.5(2)° in 2, and 105.4(6)–113.6(6)° in 3.
On the other hand, the dihedral angle for the two benzene rings
spans a wide range: 71.2 and 76.4° in 1, 82.5° in 2, and 76.5° in
3. The semi-rigid character of the tetracarboxylate molecule is
helpful for crystal growth. The bpp molecule is expected to serve
as a linker in the compounds. However, in most reported com-
pounds, it acts as a templating agent, similar to the situations
observed in 1 and 2 [51–53]. Only in limited examples does the
bpp molecule act as a linker, as found in the compound [Cu4I4(-
bpp)2] [54]. In the reported compounds [H2(bpp)][Mn2(cpph)2(H2-
O)2] (cpph = 4-(4-carboxyphenoxy)phthalate) [46] and [H2(bpp)]
3.4.2. Powder XRD patterns of 1–3
Fig. 5 presents the experimental and simulated powder XRD
patterns of 1–3. The experimental powder XRD pattern for each
compound is in accord with the simulated one generated on the
basis of the structural data, confirming that the as-synthesized
product is pure phase.
[Mn2(bcbob)2]
(bcbob = 3,5-Bis((40-carboxylbenzyl)oxy)ben-
zoilate) [48], the bpp molecule acts as a guest molecule. The forma-
tion of these two 3-D porous networks should be related to the

130
J.-J. Huang et al. / Polyhedron 117 (2016) 126–132
(a)
(b)
Fig. 3. 1-D chain (a) and 2-D supramolecular layer network (b) in 3 (a: ꢁx + 2, ꢁy + 2, ꢁz; b: x ꢁ 1, y ꢁ 1, z; c: x + 1, y, z).
100
80
60
40
20
0
1
2
3
simulated
experimental
3
2
1
200
400
600
800
0
10
20
30
40
50
Temperature( oC)
Fig. 4. TG curves of 1–3.
Two theta degree
Fig. 5. Powder XRD patterns of 1–3.
3.5. Properties
3.5.1. Photoluminescence property of 1
The solid-state photoluminescence behavior of 1 at room tem-
perature was investigated. As shown in Fig. 6 and 1 possesses pho-
toluminescence, exhibiting a blue-light emission with a maximum
at 415 nm when excited at 355 nm. Compared to the emission at
356 nm for free H4sph (kex = 292 nm) [55], the emission of 1 should
also be assigned to ligand-centered electronic excitation
), even though a larger red shift of 59 nm is observed.
The red shift should be due to the coordination of sph to the metal
center. For the other reported sph-containing complexes, a red-
shift phenomenon is also observed [56–58].
a
(
p⁄
? p

J.-J. Huang et al. / Polyhedron 117 (2016) 126–132
131
4. Conclusion
415
355
In summary, we have reported the synthesis and structural
characterization of three new semi-rigid tetracarboxylate-coordi-
nated transition-metal CPs. Synthetically, the pH value of the reac-
tion system plays a key role. It not only influences the crystal
growth, but also influences the existing forms of the organic acid
and base molecules. Structurally, the tetracarboxylate molecules
in 1–3 exhibit a semi-rigid character in the formation of the net-
work structures. The organic base molecule can assist the organic
acid molecule to construct the new CP network. The bpp molecule
tends to act as a countercation in the CP compounds. The sph-
extended 2-D Zn2+ complex displays photoluminescence, whereas
the oph-propagated 2-D Ni2+ complex shows antiferromagnetism.
Acknowledgements
300
400
500
600
700
This research was supported by the National Natural Science
Foundation of China (No. 21271083).
Wavelength ( nm )
Fig. 6. Photoluminescence excitation (green) and emission (red) spectra of 1. (Color
online.)
Appendix A. Supplementary data
CCDC 1469986–1469988 contain the supplementary crystallo-
graphic data for 1–3 respectively. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/10.
1016/j.poly.2016.05.054.
3.5.2. Magnetic property of 2
Magnetic susceptibility data were determined over the temper-
ature of range 2–300 K at a magnetic field of 1000 Oe on a Quan-
tum Design MPMS-7 SQUID magnetometer. The magnetic
behavior of 2 is depicted in the form of v
MT and vMꢁ1 versus T plots
(see Fig. 7). The experimental
vMT product at 300 K is
1.723 emu K molꢁ1, slightly lower than the theoretically expected
References
value of 2 emu K molꢁ1 for two non-interacting Ni2+ ions (S = 1/2,
g = 2.0). Upon cooling down, the
vMT value basically shows a
[1] L. Aboutorabi, A. Morsali, Coord. Chem. Rev. 310 (2016) 116.
[2] D. Bradshaw, S. El-Hankari, L. Lupica-Spagnolo, Chem. Soc. Rev. 43 (2014)
5431.
[3] C. Pettinari, A. Ta˘ba˘caru, S. Galli, Coord. Chem. Rev. 307 (2016) 1.
[4] P.C. Silva, S.M.F. Vilela, J.O.P.C. Tome, F.A.A. Paz, Chem. Soc. Rev. 44 (2015)
6774.
[5] P. Wei, X. Yan, F. Huang, Chem. Soc. Rev. 44 (2015) 815.
[6] P.C. Cheng, Y.C. Lo, W. Hsu, K.B. Thapa, S.M. Liou, J.D. Chen, Polyhedron 96
(2015) 1.
[7] Z. Xiao, X. Yang, S. Zhao, D. Wang, Y. Yang, L. Wang, J. Solid State Chem. 234
(2016) 36.
decreasing tend within the whole temperature range, suggesting
that antiferromagnetic interactions exist between the Ni2+ ions in
2. Only in the narrow temperature range of 16–11 K, does the
vMT product exhibit
a
slight increase from 0.397 to
0.411 emu K molꢁ1. This should be unconnected to the spin-cant-
ing effect, because only a minor increase by 0.014 emu K molꢁ1 is
observed. The carboxylate-bridged Ni2+ chain in 2 should be
responsible for its antiferromagnetic property, providing an effec-
tive path for magnetic exchange.
[8] Q. Yue, Q. Huang, Y.Y. Gao, E.Q. Gao, Inorg. Chim. Acta 443 (2016) 110.
[9] S. Zhang, Q. Yang, X. Liu, X. Qu, Q. Wei, G. Xie, S. Chen, S. Gao, Coord. Chem. Rev.
307 (2016) 292.
[10] O. Hietsoi, A.S. Filatov, C. Dubceac, M.A. Petrukhina, Coord. Chem. Rev. 295
(2015) 125.
[11] Q.Y. Li, Y. Quan, W. Wei, J. Li, H. Lu, R. Ni, X.J. Wang, Polyhedron 99 (2015) 1.
[12] Y. Li, N. Wang, Y.J. Xiong, Q. Cheng, J.F. Fang, F.F. Zhu, Y. Long, S.T. Yue, New J.
Chem. 39 (2015) 9872.
2.0
[13] X. Wang, J. Zhao, Y. Zhao, H. Xu, X. Shen, D.R. Zhu, S. Jing, Dalton Trans. 44
(2014) 9281.
200
1.8
[14] P.F. Shi, H.C. Hu, Z.Y. Zhang, G. Xiong, B. Zhao, Chem. Commun. 51 (2015) 3985.
[15] T. Grancha, A. Acosta, J. Cano, J. Ferrando-Soria, B. Seoane, J. Gascon, J. Pasan, D.
Armentano, E. Pardo, Inorg. Chem. 54 (2015) 10834.
[16] R. Wang, X.Y. Dong, H. Xu, R.B. Pei, M.L. Ma, S.Q. Zang, H.W. Hou, T.C.W. Mak,
Chem. Commun. 50 (2014) 9153.
[17] Q. Tang, S. Liu, Y. Liu, D. He, J. Miao, X. Wang, Y. Ji, Z. Zheng, Inorg. Chem. 53
(2014) 289.
[18] L. Liu, C. Huang, X. Xue, M. Li, H. Hou, Y. Fan, Cryst. Growth Des. 15 (2015)
4507.
[19] B. Liu, Y.H. Jiang, Z.S. Li, L. Hou, Y.Y. Wang, Inorg. Chem. Front. 2 (2015) 550.
[20] T. Grancha, J. Ferrando-Soria, H.C. Zhou, J. Gascon, B. Seoane, J. Pasan, O. Fabelo,
M. Julve, E. Pardo, Angew. Chem., Int. Ed. 54 (2015) 6521.
[21] T. Kajiwara, M. Fujii, M. Tsujimoto, K. Kobayashi, M. Higuchi, K. Tanaka, S.
Kitagawa, Angew. Chem., Int. Ed. 55 (2016) 2697.
[22] B.F. Abrahams, A.D. Dharma, B. Dyett, T.A. Hudson, H. Maynard-Casely, C.J.
Kingsbury, L.J. McCormick, R. Robson, A.L. Sutton, K.F. White, Dalton Trans. 45
(2016) 1339.
[23] R.S. Pillai, V. Benoit, A. Orsi, P.L. Llewellyn, P.A. Wright, G. Maurin, J. Phys.
Chem. C 119 (2015) 23592.
[24] R.A. Agarwal, S. Mukherjee, Polyhedron 106 (2016) 163.
[25] L. Wen, X. Wang, H. Shi, K. Lv, C. Wang, RSC Adv. 6 (2016) 1388.
[26] B. Gole, A. Kumar, P.S. Mukherjee, Chem. Eur. J. 20 (2014) 2276.
180
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
160
140
120
100
80
60
χ
χMT
1/χM
40
χ
20
0
0
50
100
150
200
250
300
T (K)
Fig. 7. Temperature dependence of
online.)
v
MT (black) and vꢁM1 (blue) vs. T for 2. (Color

132
J.-J. Huang et al. / Polyhedron 117 (2016) 126–132
[27] C. Zhang, Y. Yan, Q. Pan, L. Sun, H. He, Y. Liu, Z. Liang, J. Li, Dalton Trans. 44
[42] R. Mishra, M. Ahmad, M.R. Tripathi, R.J. Butcher, Polyhedron 50 (2013) 169.
[43] X. Hou, S.F. Tang, RSC Adv. 4 (2014) 34716.
(2015) 13340.
[28] L. Li, J.Y. Zou, S.Y. You, Y. Hu, Q.R. Ji, K.H. Chen, J.Z. Cui, Inorg. Chem. Commun.
[44] P. Thuéry, B. Masci, J. Harrowfield, Cryst. Growth Des. 13 (2013) 3216.
[45] J.J. Huang, W. Xu, Y.N. Wang, J.H. Xu, P. Zhang, J.Q. Xu, J. Solid State Chem. 226
(2015) 206.
60 (2015) 111.
[29] W.H. Huang, J.Z. Li, T. Liu, L.S. Gao, M. Jiang, Y.N. Zhang, Y.Y. Wang, RSC Adv. 5
(2015) 97127.
[46] Y.N. Wang, P. Zhang, J.H. Yu, J.Q. Xu, Dalton Trans. 44 (2015) 1655.
[47] Y.N. Wang, J.H. Yu, J.Q. Xu, ChemPlusChem 80 (2015) 1732.
[48] J.J. Huang, X. Zhang, Q.S. Huo, J.H. Yu, J.Q. Xu, Inorg. Chem. Front. 3 (2016) 406.
[49] Y.N. Wang, W.C. Zhu, Q.S. Huo, J.H. Yu, J.Q. Xu, Spectrochim. Acta A 161 (2016)
138.
[50] G.M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr. 64 (2008) 112.
[51] H.L. Jia, M.J. Jia, H. Ding, J.H. Yu, J. Jin, J.J. Zhao, J.Q. Xu, CrystEngComm 14
(2012) 8000.
[30] Y.L. Hou, H. Xu, R.R. Cheng, B. Zhao, Chem. Commun. 51 (2015) 6769.
[31] Y.C. Ou, X. Gao, Y. Zhou, Y.C. Chen, L.F. Wang, J.Z. Wu, M.L. Tong, Cryst. Growth
Des. 16 (2016) 946.
[32] M.X. Zheng, X.J. Gao, C.L. Zhang, L. Qin, H.G. Zheng, Dalton Trans. 44 (2015)
4751.
ˇ
[33] J.Z. Qiu, Y.C. Chen, L.-F. Wang, Q.W. Li, M. Orendác, M.L. Tong, Inorg. Chem.
Front. 3 (2016) 150.
[34] X.Q. Wu, M.L. Han, G.W. Xu, B. Liu, D.S. Li, J. Zhang, Inorg. Chem. Commun. 58
(2015) 60.
[52] J.J. Zhao, X. Zhang, Y.N. Wang, H.L. Jia, J.H. Yu, J.Q. Xu, J. Solid State Chem. 207
(2013) 152.
[35] L. Zhang, L. Liu, C. Huang, X. Han, L. Guo, H. Xu, H. Hou, Y. Fan, Cryst. Growth
Des. 15 (2015) 3426.
[36] A. Bajpai, P. Chandrasekhar, S. Govardhan, R. Banerjee, J.N. Moorthy, Chem.
Eur. J. 21 (2015) 2759.
[53] H.L. Jia, M.J. Jia, G. Zeng, J. Jin, J.H. Yu, J.Q. Xu, CrystEngComm 14 (2012) 6599.
[54] Q. Hou, M.J. Jia, J.J. Zhao, J. Jin, J.H. Yu, J.Q. Xu, Inorg. Chim. Acta 384 (2012) 287.
[55] G.X. Liu, K. Zhu, H.M. Xu, S. Nishihara, R.Y. Huang, X.M. Ren, CrystEngComm 12
(2012) 1175.
[37] Y. Fan, C.D. Si, C. Hou, X.Q. Yao, D.C. Hu, Y.X. Yang, J.C. Liu, Polyhedron 98
(2015) 64.
[56] G.X. Liu, R.Y. Huang, L.F. Huang, X.J. Kong, X.M. Ren, CrystEngComm 11 (2009)
643.
[38] Y.S. Yue, Y. He, L. Zhou, F.J. Chen, Y. Xu, H.B. Du, X.Z. You, B. Chen, J. Mater.
Chem. A 1 (2013) 4525.
[57] X.M. Gao, D.S. Li, J.J. Wang, F. Fu, Y.P. Wu, H.M. Hu, J.W. Wang, CrystEngComm
10 (2008) 479.
[39] L. Zhou, J. Zhang, Y.Z. Li, H.B. Du, CrystEngComm 15 (2013) 8989.
[40] T. Wang, C. Zhang, Z. Ju, H. Zheng, Dalton Trans. 44 (2015) 6926.
[41] S. Sen, S. Neogi, A. Aijaz, Q. Xu, P.K. Bharadwaj, Dalton Trans. 43 (2014) 6100.
[58] G.P. Yang, R.T. Liu, C. Ren, L. Hou, Y.Y. Wang, Q.Z. Shi, Inorg. Chim. Acta 394
(2013) 58.