A Novel 4-Connected Zn(II) Compound with 4,4′-Oxydiphthalic Acid: Synthesis, Structure and Luminescence

Article abstract of DOI:10.1080/15533174.2013.799204

A novel Zn(II) coordination polymer, [Zn(H₂ODPT)(bpp)]n (1) (H4ODPT = 4,4′-oxydiphthalic acid, bpp = 1,3-bis(4-pyridyl)- propane), was hydrothermally synthesized by the reactions of Zn(II) nitrate, H4ODPT, and bpp. Single crystal X-ray analysis reveals that 1 is a two-dimensional (2D) layer structure. In this 2D layer structure, H4ODPT is half deprotoned into H ₂ODPT^2-. Moreover, the luminescent property of this compound was also investigated in the solid state at room temperature.

Full text of DOI:10.1080/15533174.2013.799204

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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A Novel 4-Connected Zn(II) Compound With
4,4′–Oxydiphthalic Acid: Synthesis, Structure and
Luminescence
Xin Jin a
a School of Chemistry and Chemical Engineering , Xi’an University of Arts and Sciences ,
Xi’an , P.R. China
Accepted author version posted online: 17 Dec 2013.Published online: 26 Mar 2014.
To cite this article: Xin Jin (2014) A Novel 4-Connected Zn(II) Compound With 4,4′–Oxydiphthalic Acid: Synthesis, Structure
and Luminescence, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:8, 1158-1160, DOI:
10.1080/15533174.2013.799204
To link to this article: http://dx.doi.org/10.1080/15533174.2013.799204
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:1158–1160, 2014
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.799204
A Novel 4-Connected Zn(II) Compound With
4,4ꢀ–Oxydiphthalic Acid: Synthesis, Structure
and Luminescence
Xin Jin
School of Chemistry and Chemical Engineering, Xi’an University of Arts and Sciences, Xi’an, P.R. China
its flexibility to construct various interesting interpenetrating or
self-penetrating networks have attracted our attention.[7] There-
fore, in this work, we used 4, 4ꢁ–oxydiphthalic acid and bpp as
the organic bridging ligands to assemble with Zn(II) ions under
hydrothermal conditions, and successfully isolated a new lu-
minescent coordination polymer, namely [Zn(H2ODPT)(bpp)]n
(1). In this article, we report the synthesis, structure, and lumi-
nescence of this compound.
A novel Zn(II) coordination polymer, [Zn(H2ODPT)(bpp)]n (1)
(H4ODPT = 4,4ꢀ–oxydiphthalic acid, bpp = 1,3–bis(4–pyridyl)–
propane), was hydrothermally synthesized by the reactions of
Zn(II) nitrate, H4ODPT, and bpp. Single crystal X-ray analysis
reveals that 1 is a two-dimensional (2D) layer structure. In this
2D layer structure, H4ODPT is half deprotoned into H2ODPT2−
.
Moreover, the luminescent property of this compound was also
investigated in the solid state at room temperature.
Keywords coordination polymer, 4, 4ꢁ–oxydiphthalic acid, lumines-
EXPERIMENTAL
cence
Materials and Pyhsical Measurements
All reagents and solvents employed were commercially avail-
able and used without further purification. The synthesis was
carried out in 23-mL polytetrafluoroethylene lined stainless steel
containers under autogenous pressure. Elemental analyses (C,
H, and N) were determined with an elemental Vairo EL III
analyzer. The fluorescence spectra were measured on polycrys-
talline samples at room temperature using an Edinburgh FLS920
TCSPC fluorescence spectrophotometer. Single-crystal X-ray
diffraction data for compound 1 were recorded on Oxford Xcal-
ibur E diffractometer (MoKα radiation, λ = 0.71073, graphite
monochromator) at 293(2) K.
INTRODUCTION
Design and synthesis of coordination polymers have experi-
enced explosive development in the past few decades not only
because of their intriguing topological frameworks but also be-
cause of their potential applications in the areas of luminescence,
magnetism, nonlinear optics, gas storage, and so on.[1–4] Gen-
erally speaking, the basic strategy for fabricating novel metal-
organic frameworks is to combine the transition metal ions and
organic bridging ligands under appropriate conditions.[2] As a
matter of fact, crystal engineering of desired coordination poly-
mers is still a challenge to chemists. Thus, the key factor for
constructing of coordination polymers with desired structure
and properties is the judicious selection of metal centres and or-
ganic ligands with suitable shape, functionality, flexibility, and
symmetry. Among various organic ligands, polycarboxylate lig-
ands, such as isophthalic acid, terephthalic acid, benzenetricar-
boxylic acid, and so on, have been widely used by researchers
to construct coordination polymers owing to their variety of
coordination modes and sensitivity to pH values of the carboxy-
late groups.[5,6] Recently, 4, 4ꢁ–oxydiphthalic acid because of
Synthesis of [Zn(H2ODPT)(bpp)]n (1)
A mixture of Zn(NO3)3·6H2O (0.20 mmol, 0.060 g),
H4ODPTA (0.20 mmol, 0.062 g), and bpp (0.2 mmol, 0.0396 g)
in distilled water (12 mL) was placed in a Teflon-lined stain-
less steel vessel, heated to 160◦C and held at that temperature
for 3 days, then cooled to room temperature. Colorless block
crystals were obtained. Yield: 43%. Elemental analysis: Anal.
Calcd. for C29H22N2O9Zn (%): C, 46.27; H, 1.23; N, 3.22.
Found (%):C, 46.27; H, 1.23; N, 3.22.
Crystallographic Data Collection and Structures
Determination
Suitable single crystal of 1 was carefully selected under an
optical microscope and glued to thin glass fibers. Structural
measurements were performed on a computer-controlled Ox-
ford Xcalibur E diffractometer with graphite-monochromated
Received 28 March 2013; accepted 17 April 2013.
Address correspondence to Xin Jin, School of Chemistry and Chem-
ical Engineering, Xi’an University of Arts and Sciences, Xi’an, P. R.
China. E-mail: jinxin3157@126.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.
1158

A NOVEL 4-CONNECTED Zn(II) COMPOUND WITH 4,4ꢁ–OXYDIPHTHALIC ACID
1159
TABLE 1
Crystal data and structure refinements for compound 1
Empirical formula
Temperature (K)
Crystal color
Crystal size
Formula weight
Crystal system
Space group
a (Å)
C29H22N2O9Zn
293(2)
colorless
0.20 × 0.20 × 0.20 mm3
605.86
Monoclinic
P21/n
11.637(6)
b (Å)
10.905(6)
c (Å)
21.023(12)
90.00
97.947(11)
90.00
2642(3)
α (◦)
β (◦)
γ (◦)
Volume (Å3)
Z
FIG. 1. (a) Coordination environment of compoud 1, all hydrogen atoms were
omitted for clarity (symmetry code: (a) –0.5 + x, 0.5 – y, –0.5 + z; (b) –1 +
x, y, z. (b) 2D layer structure of 1. (c) Schematic representation of 4-connected
sql topological net.
4
Density (calculated)
1.523 g/cm3
Abs. coeff. (mm−1
F(000)
)
0.990
1240
RESULT AND DISCUSSION
Refinement method
Full-matrix least-squares on
F2
Crystal Structure Description
Reflections collections
Independent reflections
θ range for data collection
h,k,l range
18062
Single-crystal X-ray diffraction analysis reveals that 1 crys-
tallizes in P21/n space group with an asymmetric unit containing
one crystallographic independent Zn(II) ion, one H2ODPTA2−
anion and one bpp ligand. The partial structure of 1 is shown
in Figure 1a. It can be clearly seen that each Zn(II) ion is
four-coordinated by two nitrogen atoms from two different bpp
ligands and three carboxylate oxygen atoms from two differ-
ent H2ODPTA2− anions. The average of Zn-O/N distance is
2.031(4) Å, 2.037(5) Å, respectively, which are comparable to
those reported Zn(II) coordination polymers.[10] In 1, H4ODPTA
is half deprotoned into H2ODPTA2−, which acts as a bidentate
ligand with its two carboxylate groups in uniform monoden-
tate mode. The dihedral angle between the two phenyl rings of
4631 (Rint = 0.1082)
2.57–25.00
−13 ≤ h ≤ 13, −11 ≤ k ≤ 12,
−25 ≤ l ≤ 24
Goodness-of-fit on F2
Final R indices
[I>2sigma(I2)]
R (all data)
Largest difference peak
and hole
1.033
R = 0.0696, wR2 = 0.2124
R = 0.0957, wR2 = 0.2395
0.626 and −0.738 Å3
Mo-Kα radiation (λ=0.71073 Å) at T = 293(2) K. Absorption
correction was made using the SADABS program.[8] The struc-
ture was solved using the direct method and refined by full-
matrix least-squares methods on F2 by using the SHELXL-97
program package.[9]
TABLE 2
Selected bond lengths (Å) and angles (◦) for compound 1
Zn(1)-O(1)
Zn(1)-N(1)
1.961(4)
2.039(5)
Zn(1)-N(2)a
Zn(1)-O(8)b
2.035(5)
2.098(5)
O(1)-Zn(1)-N(2)a 101.94(18) O(1)-Zn(1)-N(1) 118.87(19)
N(2)a-Zn(1)-N(1) 109.08(18) O(1)-Zn(1)-O(8)b 97.56(18)
N(2)a-Zn(1)-O(8)b 133.32(18) N(1)-Zn(1)-O(8)b 97.38(17)
Symmetry codes: (a): x − 1/2, −y + 1/2, z - 1/2; (b): x − 1, y, z.
FIG. 2. Emission spectrum of 1 in the solid state at room temperature.

1160
X. JIN
H2ODPTA2− is 89.197◦. Therefore, Zn(II) ions are bridged by
H2ODPTA2− and bpp into a 2D wave-like layer (Figure 1b).
If each Zn(II) is simplified into a 4-connected nodes, and each
bridged ligand (H2ODPTA2− and bpp) can be looked as linkers,
this 2D layer can be simplified into a 4-connected sql net with
the short schla¨fli symbol of {44.62} (Figure 1c).
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Photoluminescent Property
Considering the excellent photoluminescent properties of d10
metal-organic frameworks, the luminescence of 1 was inves-
tigated at room temperature. As shown in Figure 2, intense
emission maximum at 440 nm can be observed upon excita-
tion of 330 nm. According to previously reported document,
H4ODPTA showed the emission maximum at 371 nm upon ex-
citation of 339 nm.[7] Therefore, the luminescent emission of
1 may be tentatively attributed to the ligand-to-metal-charge-
transfer (LMCT).
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CONCLUSIONS
In summary, a new luminescent compound has been suc-
cessfully synthesized and characterized. The compound is a
2D wave-like layered structure and can be simplified into a
4-connected sql net with the short schla¨fli symbol of {44.62}.
7. Yang, J.X.; Zhang, X.; Cheng, J.K.; Zhang, J.; Yao, Y.G. pH influence on the
structural variations of 4,4ꢁ-Oxydiphthalate coordination polymers. Cryst.
Growth Des. 2012, 12, 333–345.
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SUPPLEMENTAL MATERIAL
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novel entangled metal-organic networks constructed from 4,4ꢁ-bis(2-
methylimidazol-1-ylmethyl)biphenyl and dicarboxylates: from polycate-
nated 2D+2D→3D frameworks to polyrotaxane-like 2D+2D→2D layer.
Cryst. Eng. Comm. 2013, 14, 7856–7860.
CCDC No. 926460 contains the supplementary crystallo-
graphic data for this article. These data can be obtained free of
charge from The Cambridge Crystallographic Data Center via
htt://www.ccdc.cam.ac.uk/data request/cif.