Synthesis, Structure, and Luminescent Property of One Zinc(II) Coordination Polymer Constructed from 1H-Benzoimidazole

Article abstract of DOI:10.1080/15533174.2014.989593

A new metal-organic coordination polymer [Zn(bm)(AcO)]_n (1), where Hbm is 1H-benzoimidazole), has been prepared and structurally characterized by IR, elemental analysis and single-crystal X-ray diffraction. Single-crystal X-ray analysis shows that it crystallizes in the monoclinic space group of P2₁/c with a = 10.8231(5) ?, b = 9.8329(4) ?, c = 8.8665(4) ?, β = 99.298(4)°, V = 931.20(7) ?³, and X = 4. The bm ligand bridges two adjacent Zn(II) with its two nitrogen atoms to form a one-dimensional chain, which further constructed 2D network through a bridge bidentate AcO^- ligand. Furthermore, luminescent property of 1 was investigated.

Full text of DOI:10.1080/15533174.2014.989593

Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry
ISSN: 1553-3174 (Print) 1553-3182 (Online) Journal homepage: http://www.tandfonline.com/loi/lsrt20
Synthesis, Structure, and Luminescent Property
of One Zinc(II) Coordination Polymer Constructed
From 1H-Benzoimidazole
Shu Hua Zhang, Ru Xia Zhao, Gui Li, Hai Yang Zhang & He Ping Li
To cite this article: Shu Hua Zhang, Ru Xia Zhao, Gui Li, Hai Yang Zhang & He Ping Li (2016)
Synthesis, Structure, and Luminescent Property of One Zinc(II) Coordination Polymer
Constructed From 1H-Benzoimidazole, Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry, 46:6, 804-808, DOI: 10.1080/15533174.2014.989593
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Date: 06 February 2016, At: 21:31

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry (2016) 46, 804–808
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2014.989593
Synthesis, Structure, and Luminescent Property of One Zinc
(II) Coordination Polymer Constructed From
1H-Benzoimidazole
SHU HUA ZHANG, RU XIA ZHAO, GUI LI, HAI YANG ZHANG, and HE PING LI
College of Chemistry and Bioengineering, Guilin University of Technology (Guangxi Key Laboratory of Electrochemistry and
Magnetochemical Functional Materials), Guilin, P. R. China
Received 3 January 2014; accepted 4 November 2014
A new metal-organic coordination polymer [Zn(bm)(AcO)]n (1), where Hbm is 1H-benzoimidazole), has been prepared and
structurally characterized by IR, elemental analysis and single-crystal X-ꢀray diffraction. Single-crystal X-ray analysis shows that it
ꢀ
ꢀ
crystallizes in the monoclinic space group of P21/c with a D 10.8231(5) A, b D 9.8329(4) A, c D 8.8665(4) A, b D 99.298(4)ꢀ, V D
ꢀ
931.20(7) A3, and Z D 4. The bm ligand bridges two adjacent Zn(II) with its two nitrogen atoms to form a one-dimensional chain,
which further constructed 2D network through a bridge bidentate AcO¡ ligand. Furthermore, luminescent property of 1 was
investigated.
Keywords: 1H-benzoimidazole, coordination polymer, crystal structure, luminescent property
Introduction
benzoimidazole such as 5,6-dimethyl-1H-benzoimidazole,[28]
5-chloro-1H-benzoimidazole,[28] 5-nitro-1H-benzoimidazole
Metal-organic frameworks (MOFs) have raised an upsurge of
(Hnbm),[29] 2-nitro-1H-imidazole (Hnm),[28,29] 5-methyl-
interest in the fields of crystal engineering and functional
1H-benzoimidazole (Hmbm),[29] 5-bromo-1H-benzoimida-
materials, due to their intriguing structural features as well as
desired properties, including sensor technology,[1–3] separation
processes,[4–6] gas storage,[7–11] luminescence,[12,13] ion
exchange,[14,15] magnetism,[16–20] and catalytic materials.[21–23]
Studies in this field have been focused on the design and con-
struction of new metal-organic frameworks and the relation-
ships between their structures and properties. Although big
progress has been achieved, it remains difficult to predict the
exact structures and compositions of the final products built
by coordination bonds and/or hydrogen bonds in crystal
engineering.[24] It is known that several factors, such as the
presence of auxiliary ligands, the coordination nature of the
metal ions, and the stoichiometries of components and reac-
tion environments, may be crucial for the rational design of
the metal-organic frameworks.[25–27] Therefore, systematic
research on this topic is still important for understanding
the roles of these factors in the formation of metal-organic
coordination polymers. In the past years, analogue of 1H-
zole,[29] 1H-benzoimidazole,[28,30] and tris((benzimidazol-2-
yl)methyl)amine[31] have been used to construct novel metal-
organic frameworks with transition metal ions. In this study,
we constructed a new zinc(II) coordination polymer [Zn(bm)
(AcO)]n (1) under solvothermal conditions. In addition,
luminescent property of 1 was measured and discussed.
Experimental
Materials and Measurements
All solvent and chemicals were commercial reagents and were
used without further purification. The elemental analysis was
performed on a PE 1700 CHN auto elemental analyzer. The
crystal structure was determined by Agilent G8910A CCD
diffractometer and SHELX crystallographic software of
molecular structure. The FT-IR spectra were recorded from
KBr pellets in the range 4000–400 cm¡1 on a Bio-Rad FTS-7
spectrometer. Luminescence spectrum was obtained with a
RF-5301PC fluorescence spectrometer.
Address correspondence to Shu Hua Zhang, College of Chemis-
try and Bioengineering, Guilin University of Technology
(Guangxi Key Laboratory of Electrochemistry and Magneto-
chemical Functional Materials), Guilin 541004, P. R. China.
E-mail: zsh720108@163.com
Synthesis of [Zn(bm)(AcO)]n (1)
The ligand (2-amino-2-(1H-benzo[d]imidazol-2-yl)ethanol
(HL)) was prepared with benzene-1,2-diamine and L-serine
according to a literature procedure.[32] The Hbm ligand was
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.

One Zinc(II) Coordination Polymer
805
ꢀ
Table 2. Metal–ligand bond lengths (A) and angles (ꢀ) in com-
plex 1
O1-Zn1i
O2-Zn1
1.983(3)
2.005(3)
1.979(3)
1.985(3)
1.983(3)
1.985(3)
125.8(3)
129.2(3)
133.4(3)
126.8(3)
128.4(3)
110.5(3)
111.79(14)
118.29(14)
114.42(13)
102.61(13)
102.79(13)
104.56(13)
N1-Zn1
N2-Zn1ii
Zn1-O1iii
Zn1-N2iv
C7-N1-Zn1
C1-N1-Zn1
C9-O2-Zn1
C7-N2-Zn1i
C6-N2-Zn1i
C9-O1-Zn1ii
N1-Zn1-O1iii
N1-Zn1-N2iv
O1iii-Zn1-N2iv
N1-Zn1-O2
O1iii-Zn1-O2
N2iv-Zn1-O2
Symmetry codes: (i) x, ¡yC1/2, z¡1/2; (ii) ¡xC1, yC1/2, ¡zC3/2; (iii) x,
¡yC1/2, zC1/2; (iv) ¡xC1, y¡1/2, ¡zC3/2.
Sch 1. Formation mechanism of Hbm.
attained through an in situ reaction (The formation mecha-
nism of Hbm see Scheme 1).
for 120 h, and then the reaction system was cooled to room
temperature. Block, colorless crystals of 1 were collected by
filtration and washed with methanol several times with a yield
of 70%. Anal. Calcd. for C9H8N2O2Zn (%): C, 44.71; H,
3.31; N, 11.59; Found: (%): C,44.66; H,3.35; N, 11.67.
The mixture of Zn(AcO)2¢2H2O (0.220 g, 1 mmol), Hbm
(0.118 g, 1 mmol) was dissolved in 10 ml methanol. The pH
was adjusted to 7.5 by addition triethylamine. Consequently,
the resulting mixture was transferred to a 25 mL Teflon-lined
stainless steel vessel, which was sealed and heated at 140ꢀC
Crystal Structure Determination
Table 1. Crystallographic data for complex 1
A Block, colorless crystal of complex 1 having approximate
dimensions 0.25 £ 0.18 £ 0.13 mm was selected and
mounted on a glass fiber. All measurements were made on a
Agilent G8910A CCD diffractometer with a ꢀgraphite-mono-
chromated Mo-Ka radiation (λ D 0.71073 A) by using the
v-u scan mode in the range of 3.12 ꢀ u ꢀ 25.10ꢀ at 298 K.
Raw frame data was integrated with the SAINT program.[33]
The structure was solved by direct methods with SHELXS-97
and refined by full-matrix least-squares on F2 using
SHELXL-97.[33] The empirical absorption correction was
applied with the program SADABS.[33] All non-hydrogen
atoms were refined anisotropically, while all hydrogen atoms
were set in the calculated positions and refined by a riding
model. The crystallographic details are provided in Table 1,
while the selected bond distances and angles are listed in
Table 2. Crystallographic data for the structural analysis
have been deposited with the Cambridge Crystallographic
Data Center. CCDC reference number for 1 is 979343.
Complex
1<
Formula
Mr
Crystal size (mm)
T (K)
Crystal system
C9H8N2O2Zn
241.56
0.25 £ 0.18 £ 0.13
293 (2)
Monoclinic
P21/c
Space group
ꢀ
a (A)
10.8231 (5)
9.8329 (4)
8.8665 (4)
99.298 (4)
931.20 (7)
488
ꢀ
b (A)
ꢀ
c (A)
b (ꢀ)
ꢀ
V (A3)
F(000)
Z
4
Dc (g cm¡3
)
1.732
2.609
m (mm¡1
u range (ꢀ)
)
3.12–25.10
5627, 1665
1273
Ref. meas. / indep.
Obs. ref.[I > 2s (I)]
Rint
Results and Discussion
0.0487
0.0407
0.0927
R1 [I ꢁ 2s (I)] a
vR2(all data)b
Crystal Structure Description
Goof
1
ꢀ
The molecular structure of complex 1 is illustrated in
Figure 1. Each Zn(II) atom is four-coordinated by two nitro-
gen atoms of two bm bridging ligands, and two oxygen atoms
from two acetato ligands, forming a distorted tetrahedron
Dr(max, min) (e A¡3
)
0.938, –0.611
aR1 D SjjFoj – jFcjj/SjFoj.
bwR2 D [Sw(jFo j– jFc j)2/Sw(jFo j)2]1/2
.
2
2
2

806
Zhang et al.
Fig. 3. IR spectra of 1.
Fig. 1. The structure of 1, all hydrogen atoms were omitted.
chain further constructs a 2-D network though the acetato
ligand. The acetato ligand also coordinates to the two Zn
geometry. The structure of 1 is similarly adopted by
[29]
[Zn2(nbm)2(nm)2]n
and
[Zn2(mbm)2(nm)2]n
and
{[Zn2(nm)2(bm)2]¢(H2O)}n.[28] The bond lengths of Zn1¡O1i
atoms in a bidentate fashion. The Zn¢¢¢Zn separation across
ꢀ
ꢀ
the bridging acetato ligand is 4.455 A, which is longer than
[1.983(3) A, symmetry: (i): x, 0.5 ꢀ¡ y, ¡0.5 C z], Zn1¡ O2
ꢀ
ꢀ
that observed in other acetato ligand polymers[35] (Zn¢¢¢Zn
[2.005(3) A], Zn1¡N1 [1.979(3) A], Zn1¡N2ii [1.985(3) A,
symmetry: (ii): ¡ x, 1 ¡ y, ¡ z] are comparable to the ones
found in {[Zn2(ipa)(bm)2]¢(H2O)}n (Hipa is isophthalic
acid).[34]
ꢀ
distance is 2.900(1)-4.162(1) A). Herein, the coordination
mode of carboxyl group is syn-anti-bidentate.[36] The C9-O
(O atoms of carboxyl group) distances are almost equaled
ꢀ
ꢀ
(C9-O1, 1.267(5) A; C9¡O2, 1.248(5) A), in accordance with
the bidentate coordination mode of carboxyl groups but that
is different from the monodentate coordination mode.[37]
Each bm ligand coordinates to two Zn (II) atoms through
its two aromatic N atoms and acts as a bridging bidentate
ligand to form an infinite 1-D chain structure (Figure 2). The
ꢀ
Zn¢¢¢Zn separation across the bridging bm is 5.923 A. Which
(H2O)}n (Zn¢¢¢Zn distance is 5.796–5.974 A).[28] The 1-D
is among the range that observed in {[Zn2(nm)2(bm)2]¢
ꢀ
IR Spectrum of 1
The IR spectral data of the compound 1 is shown in Figure 3.
There are indications that broad bands in the range of
3154 cm¡1 can be assigned to weak hydrogen bond (C8–
ꢀ
H8C¢¢¢O1i, 3.372 A, symmetry code: (i) x, 0.5 - y, 0.5 C z).
The bands of 1458 and 1400 cm¡1 are assigned to nsCOO¡
and nasCOO¡, respectively which indicate bidentate coordi-
nation mode.[38,39] The bands at 1243 cm¡1 may be assigned
to the n(C-N) stretching frequencies. The strong peak of
1548 cm¡1 for 1 may be attributed to the C D N stretching
vibration of the imidazole ring of the bm ligand. The IR attri-
bution is consistent with the crystal structure determination.
Luminescent Property of 1
Coordination polymers based on d10 metal centers and organic
ligands are promising candidates for photoactive materials with
potential applications.[40] In this study, luminescent property of
compound 1 and the free ligand has been investigated in DMF
solvent that concentrations are 4 £ 10¡6 and 6 £ 10¡5 mol¢L¡1
,
respectively. As is shown in Figure 4, excitation at 280 nm leads
to luminescent with emission maxima at 299 nm for free ligand,
309 nm for 1. The similarity between emission spectra of the
polymer and free ligand, excluding emission intensity, implies
that the luminescent signal transduction mechanism should be
ascribed to the intra-ligand p-p* and n-p* luminescent emis-
sion.[41] On the other hand, slight red shifts of 10 nm and
Fig. 2.ꢀ2-D networkꢀ of 1, all hydrogen atoms were omitted. a D
5.923 A, b D 4.455 A.

One Zinc(II) Coordination Polymer
807
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