Journal of Molecular Structure 1142 (2017) 304e310

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Three coordination polymers based on 9,10-di(pyridine-4-yl)

anthracene ligand: Syntheses, structures and fluorescent properties
Jun-Liang Dong a, Duo-Zhi Wang a, b, *, Yan-Yuan Jia c, Dan-Hong Wang d, **
a
College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, PR China
b
Key Laboratory of Energy Materials Chemistry, Ministry of Education, Institute of Applied Chemistry, Xinjiang University, Urumqi, 830046 Xinjiang, PR
China
c
Colledge of Chemistry, Nankai University, Tianjin 300071, PR China
d
School of Materials Science and Engineering, Nankai University, Tianjin 300350, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Three new mixed-ligand divalent coordination polymers (CPs) {[Zn3(L)(1,4-bdc)3]$2DMF}n (1),
Received 24 February 2017 {[Zn2(L)(2,6-ndc)2]$3DMF}n (2) and {[Cd2(L)3(2,6-ndc)2]}n (3) [L ¼ 9,10-di(pyridine-4-yl)anthracene, 1,4-
Received in revised form H2bdc ¼ 1,4-benzenedicarboxylic acid, 2,6-H2ndc ¼ 2,6-naphthalenedicarboxylic acid] have been pre-
10 April 2017
pared and well characterized by elemental analyses, infrared spectroscopy, single-crystal X-ray diffrac-
Accepted 15 April 2017
Available online 17 April 2017
tion techniques, powder X-ray diffraction patterns and thermogravimetric analyses. The crystal structure
analyses of coordination polymers (CPs) reveal that all the complexes 1e3 have the three-dimensional
(3D) coordination networks. The structure of 1 can be simplified as a sqc3 3D 8-connected framework
Keywords:
Coordination polymers
with the point symbol of (424$64). Particularly, in the presence of the linear 2,6-H2ndc auxiliary ligand, a
9,10-di(pyridine-4-yl)anthracene double-deck interpenetrating pcu 3D network of 2 is assembled by 6-connecting framework with the
Crystal structure point symbol of (412$63). Complex 3 exhibits a ttd 3D 5-connected net with a point symbol of (46$64).
Fluorescent properties Further, the solid-state luminescent properties of the complexes 1e3 were measured and studied at
room temperature.
© 2017 Published by Elsevier B.V.

1. Introduction outcome of target MOCPs [9]. Among various organic ligands, the
flexible bis(pyridine) derivatives with remarkable coordination
Over the past few decades, metal-organic coordination poly- ability and versatile conformations, have attracted great interest
mers (MOCPs) has a rocket-like speed of development, and the self- within coordination chemistry [10].
assembly of transition metal salts with mixed ligands of carbox- Recently, the mixed-ligand systems generated from poly-
ylate and multidentate N-donor have been employed to construct carboxylic acids and N-donor linkers have been widely adopted for
MOCPs displaying intriguing architectures and various potential the assembly of new coordination networks. Compared with the
applications in the fields of catalysis, luminescence, magnetism, single ligand, the mixed-ligand is more likely to form frameworks
nonlinear optics, gas storage, and so on [1e5]. The self-assembly of with the desired structure [11]. However, the MOCPs based on ar-
MOCPs with yearning for intriguing structures and properties is still omatic dicarboxylate have been extensively investigated in the past
facing many difficulties, because the structures of complexes may decades due to their strong coordination capability, large
be easily affected by organic ligands, metal ions, solvent, metal- conjugated-system and the possibility of offering new functional
ligand ratio, reaction temperature, counterions and many more materials [12e15]. The 2,6-naphthalenedicarboxylic acid (2,6-
[6e8]. Among them, the selection of suitable multifunctional li- H2ndc) and 1,4-benzenedicarboxylic acid (1,4-H2bdc) are typical
gands as building blocks is crucial to determining the structural aromatic dicarboxylic acids, which have attracted tremendous
attention in constructing MOCFs with elegant architectures and
desired properties, and they can be attributed to their various
coordinating modes, high symmetry and structural rigidity [16].
* Corresponding author. College of Chemistry and Chemical Engineering, Xinjiang In this study, we designed and synthesized such a ligand, 9,10-
University, Urumqi 830046, PR China.
** Corresponding author.
di(pyridine-4-yl)anthracene (L) (see Scheme 1), to construct coor-
E-mail address: wangdz@xju.edu.cn (D.-Z. Wang). dinative networks. On the basis of the L and two assistant

http://dx.doi.org/10.1016/j.molstruc.2017.04.057
0022-2860/© 2017 Published by Elsevier B.V.
 J.-L. Dong et al. / Journal of Molecular Structure 1142 (2017) 304e310 305

2.3. Synthesis of complexes 1~3

2.3.1. Preparation of [Zn3(L)(1,4-bdc)3]·2DMF (1)

A mixture of Zn(NO3)2$6H2O (30 mg, 0.1 mmol), L (16.6 mg,
0.05 mmol), 1,4-H2bdc (16.6 mg, 0.1 mmol) was put in a reaction
vessel (10 ml) and DMF (3 ml) was added to it, then sealed, with
ultrasonic processing for 30 min the solid completely dissolved in
DMF giving a clear solution. The reaction solution was heated at
70  C for five days then cooled to room temperature and filtered,
after the solid was washed with DMF and dried to obtain many
yellow petals crystals (ca. 51.2% yield based on L). Anal. Calcd (%) for
Scheme 1. The ligand L and organic acids used in this work.
C48H28N2O12Zn3 (%): C, 54.73; H, 3.53; N, 4.91. Found: C, 54.71; H,
3.58; N, 4.89. IR (KBr pellets, cm1): 3062(m), 2926(s), 2856(s),
1954(m), 1829(m), 1671(s), 1607(s), 1506(s), 1390(s), 1262(m),
1134(s), 1096(s), 1023(m), 951(s), 885(s), 825(s), 750(s), 644(m).
carboxylic ligands, 1,4-H2bdc and 2,6-H2ndc (see Scheme 1), we got
three complexes: namely, {[Zn3(L)(1,4-bdc)3]$2DMF}n (1),
2.3.2. Preparation of [Zn2(L)(2,6-ndc)2]·3DMF (2)
{[Zn2(L)(2,6-ndc)2]$3DMF}n (2), and {[Cd2(L)3(2,6-ndc)2]}n (3). All
The preparation of complex 2 was similar to that of 1, except that
complexes were structurally characterized by elemental analyses,
2,6-H2ndc (21.6 mg, 0.1 mmol) was used instead of 1,4-H2bdc
IR spectra, single crystal X-ray diffraction techniques and powder
(16.6 mg, 0.1 mmol), and heated at 95  C for four days. Resulting in
X-ray diffraction patterns (PXRD). As we known, the topological
the formation of orange square crystals of 2 that were obtained.
analyses of complexes can simplify complicated frameworks of
Yield: 62.1% based on L. Anal Calcd (%) for C117H105N11O23Zn4 (%): C,
coordination polymers, and it plays an instructive role in the
61.69; H, 4.36; N, 5.05. Found: C, 61.63; H, 4.37; N, 5.02. IR
rational design of some predicted functional materials [17]. In the
(KBrpellets, cm1): 3300(m), 3055(m), 2933(s), 1949(m), 1662(s),
present work, topological analyses reveal that complexes 1e3
1608(s), 1514(m), 1457(m), 1418(s), 1358(s), 1259(s), 1217(s),1158(s),
display three-dimensional (3D) frameworks with different topo-
1091(s), 1068(s), 1030(s), 859(m), 824(s).
logical structures. Furthermore, the photoluminescence properties
and thermal stabilities have been investigated.
2.3.3. Preparation of [Cd2(L)3(2,6-ndc)2] (3)
The preparation of complex 3 was similar to that of 1, except that
2. Experimental section Cd(NO3)2$4H2O (31 mg, 0.1 mmol) was used instead of
Zn(NO3)2$6H2O (30 mg, 0.1 mmol), and heated at 95  C for 3 days.
2.1. Materials and measurements Resulting in the formation of yellow particles and crystals of 3 were
obtained. Yield: 50.5% based on L. Anal Calcd (%) for C48H30N3O4Cd
All reagents and solvents were commercially available and used (%): C, 69.87; H, 3.66; N, 5.09. Found: C, 69.85; H, 3.68; N, 5.07. IR
without further purification. FT-IR spectra were recorded by a (KBrpellets, cm1): 3320(m), 3057(s), 2933(s), 1956(m), 1834(m),
Thermo Scientific Nicolet 6000 FT-IR spectrophotometer with KBr 1654(s), 1603(s), 1564(s), 1491(s), 1400(s), 1359(s), 1219(s), 1192(s),
pellets in the 400-4000 cm1 region. Elemental analyses for C, H, 1143(s), 1097(s), 1013(s), 931(s), 797(s).
and N were performed by Perkin-Elmer 240 analyzer. Powder X-ray
diffraction (PXRD) data were recorded on a Rigaku D/Max-2500 2.4. X-ray crystallography
diffractometer. Thermogravimetric analyses were carried out by
the Japan's neo-confucianism standard TG-DTA analyzer. The Single-crystal X-ray data for complexes 1e3 were collected with
fluorescent spectra were carried out by Hitachi F-4500 fluorescence a Bruker APEX2 Smart CCD diffractometer using Mo-Ka
spectrometer. (l ¼ 0.71073 Å) radiation at room temperature. All the structures
were solved by direct methods and refined by the full-matrix least-
squares methods on F2 using the SHELXTL software [18]. Metal
2.2. Preparation of ligand L atoms in the complexes were located from the E-maps and other
non-hydrogen atoms were located in successive difference Fourier
9,10-dibromoanthracene (2.0 g, 5.95 mmol), Pyridine-4-boronic syntheses by refining with anisotropic thermal parameters on F2.
acid (2.4 g, 17.8 mmol), K2CO3 (11.6 g, 35.5 mmol), Pd(PPh3)4 (0.68 g, All of the hydrogen atoms were placed in the calculated position.
0.59 mmol) and PhMe:DMF (6:1, 300 ml) were successively add to a Crystallographic datas and experimental details for structure
500 ml flask. Under N2 conditions, the reaction mixture was heated determination are presented in Table 1. Selected bond lengths and
to 130  C in the dark for 48 h. After the reaction mixture was cooled bond angles are listed in Table S1 of Supplementary 1.
to room temperature and filtered to remove the catalyst by diato-
maceous earth. The removal of solvent under reduced pressure 3. Results and discussion
yielded crude solid. The crude solid was dissolved in dichloro-
methane and washed with distilled water, then dried over anhy- 3.1. Syntheses and general characterization
drous magnesium sulfate and concentrate dichloromethane under
reduced pressure. A HCl solution was added and adjusted the pH to Despite solvothermal reaction being in a “black box” and being
2e3. Solid precipitation was produced and then filtered, the solid somewhat complicated, it has been proven to be an effective
was dissolved in water and adjusted the pH to 8e9 by the addition method in preparing MOCPs. A series of experiments were carried
of NaOH (10 M) solution. The pale yellow solid thus obtained by out in order to get the optimal reaction temperatures and solvents
filtration and was washed with distilled water. Yield (1.4 g, 70%). MS for single crystal growth. Herein, complexes 1e3 were successfully
(333.1387). 1H NMR (CDCl3-d6, dppm): 8.879 (m, 4H, pyridine-2), prepared by solvothermal reactions at 70e95  C. The crystal
7.609 (m, 4H, anthracene-1), 7.456 (m, 4H, pyridine-3), 7.405 (t, structures of these coordination polymers were analyzed in terms
4H, anthracene-2). of network geometries, the thermogravimetric analyses and
306 J.-L. Dong et al. / Journal of Molecular Structure 1142 (2017) 304e310

Table 1
Crystal data and structure refinement summary for complexes 1e3.

1 2 3

Formula C52H40N4O14Zn3 C57H48N5O11Zn2 C96H60N6O8Cd2

Formula wt 1141.05 1109.78 1650.32
Crystal system Monoclinic Triclinic Triclinic
Space group C2/c P-1 P-1
T (K) 386(2) 386(2) 386(2)
a (Å) 42.213(3) 12.997(3) 9.1668(12)
b (Å) 9.4323(9) 13.106(3) 13.6510(16)
c (Å) 46.063(3) 17.213(4) 22.598(3)
a ( ) 90 93.895(4) 74.887(5)
b ( ) 156.243(2) 107.639(6) 84.345(6)
g ( ) 90 95.018(6) 88.071(8)
V (Å3) 7388.7(10) 2769.6(12) 2716.6(6)
Z 4 1 2
D (Mg/m3) 0.918 1.376 1.009
m (mm1) 1.006 0.932 0.437
F(000) 2064 1188 838
Crystal size (mm3) 0.22  0.20  0.18 0.22  0.20  0.18 0.22  0.20  0.18
Theta rang (deg) 3.12e27.52 3.00e27.53 3.05e27.55
Goof(F2) 0.810 0.990 1.194
Messuredrefins 45774 35205 34869
Obsdreflns 8455 12435 12238
Rint 0.0321 0.0290 0.0192
Ra/wRb 0.0625/0.1453 0.0578/0.1547 0.0363/0.1105
a
R ¼ S(jjF0j¡jFCjj)/SjF0j.
b
wR ¼ [Sw(jF0j2¡jFCj2)2/Sw(F20)]1/2.

fluorescence properties were studied on base of their structural axial location of octahedral (Fig. 1b). Three Zn(II) ions (Zn1, Zn2 and
aspects. The pertinent crystallographic details for complexes 1e3 Zn1#5) are bridged by m2-1,3-carboxylate and m2-carboxylate oxy-
were given in Table 1 and Table S1 respectively. gen atoms to form a trimer (Fig. 1c), with the Zn/Zn distance is
The infrared spectra of 1e3 exhibit characteristic absorption for 3.205 Å. The dihedral angle between one pyridine ring and one
corresponding ligand with a slight shift due to coordination. For anthracene ring in the same L is 63.9 . The trimers are joined
complexes 1e3, the weak bands observed in the range 3064- through the scaffolds of 1,4-H2bdc ligands, leading to the formation
2922 cm1 are attributed to aromatic stretching vibrations. The of a 44-sqc coordination layer and two trimers in a diagonal posi-
bands observed at 1675 and 1358 cm1 are due to asymmetric and tion are linked by 1,4-H2bdc (Fig. 1d). The L ligand adopts bidentate
symmetric stretching vibrations of carboxylate groups in H2bdc and bridging coordination, linking the 2D layers to form a 3D frame-
H2ndc, respectively. The asymmetric vibration at 1675 cm1 of work (Fig. 1e). Meanwhile, from the topological point of view, Zn2
H2bdc and H2ndc disappeared after conversion to complexes 1e3, can be described as 8-connected nodes, and the ligands are regar-
indicating the full deprotonation of carboxylate groups in H2bdc ded as linear linkers. Thus, the structure of 1 can be simplified as a
and H2ndc. 3D 8-connected framework with the point symbol of (424$64)
(Fig. 1f).
3.2. Description of the crystal structure
3.2.2. Structure of {[Zn2(L)(2,6-ndc)2]·3DMF}n (2)
3.2.1. Structure of {[Zn3(L)(1,4-bdc)3]·2DMF}n(1) Single crystal X-ray diffraction analysis reveals that complex 2
X-ray crystallographic analysis shows that complex 1 crystal- crystallizes in the triclinic space group P-1 and features a 3D
lizes in the monoclinic space group C2/c and features a 3D frame- framework structure. The complex 2 contains two Zn(II) ions, one L
work structure, and it consists of three Zn(II) ions (Zn1, Zn2 and ligand, two 2,6-ndc2- anions and three uncoordinated DMF mole-
Zn1#5, symmetry code: #5 -xþ1,-y,-zþ1), one L ligand, three bdc2 cules. The all Zn(II) ions are five coordinated with a slightly dis-
anions and two uncoordinated DMF molecules. The Zn(II) ions torted quadrangular pyramid coordination geometry, which is
show different coordination geometries. The Zn1 (Zn1#5) ion is five coordinated by four O atoms (O2, O3, O5, and O7) originating from
coordinated with a distorted pentahedron coordination geometry, four independent 2,6-ndc2- anions and one N atom (N1) from L
which is fulfilled by four oxygen atoms (O1, O2, O4 and O5) origi- ligand with the coordination angles varying from 87.3(5) to
nating from three independent 1,4-H2bdc ligands and one nitrogen 110.4(3) (Fig. 2a). The four oxygen atoms are located in the equa-
atom (N1) of the L ligand with the coordination angles varying from torial plane of quadrangular pyramid and are coplanar, and the N1
99.9(9) to 121.9(6) . The ZneN bond length is 2.004(3) Å, and the atom is in the axial location of quadrangular pyramid. The ZneN
lengths of ZneO bonds are 1.975(3) Å, 1.955(3) Å and 1.930(3) Å, bond lengths are 2.027(3) Å and 2.035(3) Å, respectively, and the
respectively, four oxygen atoms and one nitrogen atom are located lengths of ZneO bond lengths range from 2.021(3) Å to 2.079(2) Å.
on the five vertices of pentahedron, and the Zn1(Zn1#5) is located in Two adjacent Zn ions are bridged by m2-1,3-carboxylate to form a
the center of pentahedron (Fig. 1a). The Zn2 center is six coordi- dimer and the Zn/Zn distance is 2.977 Å. The dihedral angle be-
nated by six O atoms from six 1,4-bdc2- ions to complete an octa- tween one pyridine ring and one anthracene ring in the same L is
hedral geometry with the coordination angles varying from 63.9 . However, the dimers are joined through the scaffolds of 2,6-
81.9(6) to 120.0(0) . The ZneO bond lengths are 2.036(3) Å, H2ndc ligands, leading to the formation of a 44-pcu coordination 2D
2.058(3) Å and 2.181(3) Å, severally. The four oxygen atoms (O3, layer (Fig. 2b), which is different with complex 1. In complex 2, the
O3#5, O6, and O6#5) are located in the equatorial plane location of distance between adjacent dimers is equal and the two dimers in
octahedral and the two oxygen atoms (O1, O1#5) are located in the the diagonal position are not linked by the 2,6-H2ndc ligands. Then
 J.-L. Dong et al. / Journal of Molecular Structure 1142 (2017) 304e310 307

Fig. 1. View of (a) (b) and (c) the coordination environment of Zn(II) atoms in complex 1; (d) the 2D sheet structure of 1; (e) the 3D architecture of 1; (f) the 8-connected net
topology with the Schla €fli symbol of (424$64).

the 2D layer is bridged to give 3D framework by L ligands (Fig. 2c). planes is 32.31 ), while N1 and N2 occupy axial positions with the
For a better understanding of the intricate framework, a topo- N1eCdeN2 bond angle of 172.20(3) . The Cd(II) ions are connected
logical analysis of complex 2 was performed. In the 2D layer, we can by 2,6-H2ndc ligands to generate a 44-ttd coordination 2D layer
define the [Zn2(L)(2,6-ndc)2] dimer as six-connected nodes with all (Fig. 3b), which is further bridged to form 3D framework by L li-
crystallographically independent L ligands and 2,6-ndc2- anions as gands (Fig. 3c). In contrast, in complex 3, the difference of 44-ttd
linkers. Thus, the network topology of 2 can be represented as a with those complexes of 1 and 2 is a ladder-like structure. From the
two-dimensional layer interpenetrating 6-connected framework viewpoint of structure topology, Cd(II) ions can be considered as 5-
with the point symbol of (412$63) (Fig. 2d). connected nodes, the L and 2,6-ndc2- anions are simply viewed as
linkers. Therefore, the whole 3D framework should be simplified as
3.2.3. Structure of {[Cd2(L)3(2,6-ndc)2]}n (3) a 5-connected net with a point symbol of (46$64) (Fig. 3d).
Single crystal X-ray diffraction structural analysis reveals that
complex 3 crystallizes in the triclinic space with group P-1 and 3.3. Powder X-ray diffraction (PXRD) and thermogravimetric
features a 3D net. Complex 3 includes an asymmetric unit con- analysis
sisting of one Cd(II) ion, one and half of L ligands and one 2,6-ndc2-
anion, As shown in Fig. 3a, each Cd(II) ion is coordinated by three PXRD is a reliable technique to characterize the nature of the
nitrogen atoms (N1, N2, N3) from three different L ligands (CdeN new solid forms in crystallization experiment. The PXRD experi-
2.361(2) Å, 2.377(2) Å and 2.444(2) Å) and four oxygen atoms (O1, mental and computer-simulated patterns of the corresponding
O2, O3 and O4) from two 2,6-ndc2- anions (CdeO 2.253(2)-2.697(2) complexes were shown in Supplementary 2 Fig. S1, which showed
Å) to generate a distorted pentagonal bipyramid geometry with the good agreement with that of the simulated ones, indicating that
coordination angles varying from 55.29(7) to 119.95(9) , and the the as-synthesized products are in pure phase. The preferred
equatorial plane is occupied by the above four oxygen atoms and orientation of the powder sample may cause the differences in
one nitrogen atom (N3) (the O1, O2 and O3 are coplanar, the O1, O4 intensity.
and N3 are coplanar, and the dihedral angle between two different For the sake of researching the framework stability of the
308 J.-L. Dong et al. / Journal of Molecular Structure 1142 (2017) 304e310

€fli symbol
Fig. 2. View of (a) the coordination environment of Zn(II) atoms in complex 2; (b) the 2D sheet of 2; (c) the 3D sheet of 2; (d) the 6-connected net topology with the Schla
of (412$63).

complexes 1e3 were shown in Supplementary 2 Fig. S2. The TG experimental condition and their emission spectra are given in
shows that the complex 2 undergoes decomposition in two stages, Supplementary 2 Fig. S3. When excited with 390 nm light, the free L
and the complex 3 undergoes decomposition in three stages [19]. ligand exhibited an emission peak at 470 nm, which originated
For 1, in the whole process of stepwise decomposition until the from ligand internal change transfer. Upon excitation with 390 nm
temperature rise to 500  C, the final residual of 19.05% may be the light, complexes 1e3 all display intense photoluminescence, with
mixture of ZnCO3 and ZnO (Calcd 20.17%). For 2, the first loss of emission maxima at 474, 440 and 440 nm, respectively. Compared
39.34%, occurs between 25  C and 150  C, corresponding to the loss with the free L Ligand, the introduction of Zn(II) and Cd(II) to ligand
of three lattice DMF molecules and two L molecules (Calcd 38.49%). L led to a weak blue-shift for complexes 2 and 3. On the one hand,
The second that occurs between 300 and 475 are ascribed to the because the N atoms coordination to the metal center, the electron
collapse of the framework. The final residual of 9.08% may be the transfer to the metal ions and occurs Ligand-to-Metal Charge
mixture of ZnCO3 and ZnO (Calcd 7.33%). For 3, the first loss, of Transition (LMCT). Moreover, the ligand p* track as the highest
9.42%, occurs between 25  C and 80  C, corresponding to the loss of occupied molecular orbital (HOMO) and the metal d track for the
one lattice DMF molecule (Calcd 9.02%). The second occurs be- lowest unoccupied molecular orbital (LUMO), the electron transfer
tween 130  C and 240  C, amounting to about 10.09%, corre- when subjected to external excitation, resulting in the maximum
sponding to escape of one lattice DMF molecule (Calcd 9.02%), and absorption wavelength of the compounds blue shift. On the other
the third weight loss between 350  C and 500  C amounts to about hand, the differences of the peaks for 1 may be resulted from
60.02%, which is ascribed to the collapse of the framework (Calcd different coordination environments around Zn(II) and Cd(II) cen-
60.35%), and the final residual of 19.37% may be CdCO3 (Calcd ters [21]. In addition, the high-dimensional structures of complexes
20.84%). 2 and 3 lead to significant enhancement of fluorescence intensity
compared to that of the free ligand. The enhancement of fluores-
3.4. Fluorescent properties cence intensity of complexes 1e3 can be attributed to the following
aspects: firstly, anthracene is a kind of polycyclic aromatic hydro-
It is known that many d10 metal complexes exhibit lumines- carbons with strong fluorescence emission; secondly, the ligand
cence properties. The coordination complexes with the rational coordination to the metal center and increase plane conjugated
selection and design of conjugated organic spacers with metal system of ligands, which the intraligand p / p* transition occurs
centers can be efficient for obtaining new luminescent materials more easily; on the other hand, the ligand rigidity enhancement
[20]. To investigate the luminescence properties of complexes 1e3, and thus reduces the loss of energy through a radiationless
the solid-state fluorescent properties of 1e3 as well as the ligand L pathway [22], however, fluorescence enhancement of complexes
have been studied at room temperature under the same 1e3.
 J.-L. Dong et al. / Journal of Molecular Structure 1142 (2017) 304e310 309

4. Conclusion

In summary, three new Zn(II)/Cd(II) complexes with 9,10-

di(pyridine-4-yl)anthracene have been successfully constructed
and characterized by single-crystal X-ray diffraction, element
analysis, IR and PXRD. Complexes 1e3 have the 3D network
structure. The central metals, reaction solvents and temperatures
play crucial roles in the formation of complexes 1e3. The X-ray
powder diffraction (PXRD) of the complexes 1e3 demonstrate that
they have high phase purity. In addition, we studied thermal sta-
bilities and fluorescent properties of complexes 1e3. We believe
that this study reveals the effectiveness of general solvothermal
processing methods which are influenced by the nature of the
solvent and reaction temperature. Because of the multi ring
structure of the ligand molecule, the solubility of the ligand is
reduced and the difficulty coefficient is enhanced. Complexes 1e3
has a novel structure and strong fluorescence properties, which
indicated that those complexes can be used as a potential func-
tional materials, for example used in LED lamps. For another, the
coordination of the carboxylate group from auxiliary ligand to
metal center effectively increase the dimension of the coordination
polymers, which provides a potential guiding significance for the
synthesis of coordination polymers with multi dimensions.

Acknowledgments

This work was financially supported by the National Nature

Science Foundation of China (No. 21361026).

Appendix A. Supplementary data

Supplementary data related to this article can be found at http://

dx.doi.org/10.1016/j.molstruc.2017.04.057.

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