Syntheses, structures and photoluminescent properties of two zinc(II) coordination polymers based on aromatic polycarboxylate and 1,4-bis(imidazol-1-ylmethyl)benzene

Article abstract of DOI:10.1016/j.ica.2009.09.014

Hydrothermal reaction of Zn(NO₃)₂·6H₂O with benzene-1,2,3-tricarboxylic acid (H₃BTC) or 5-bromoisophthalic acid (H₂BIPA) in the presence of 1,4-bis(imidazol-1-ylmethyl)benzene (bix) produced two novel

Full text of DOI:10.1016/j.ica.2009.09.014

Inorganica Chimica Acta 362 (2009) 5103–5108
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Inorganica Chimica Acta
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Syntheses, structures and photoluminescent properties of two zinc(II)
coordination polymers based on aromatic polycarboxylate
and 1,4-bis(imidazol-1-ylmethyl)benzene
a
b
a,
a
Guang-Xiang Liu a, , Kun Zhu , Sadafumi Nishihara , Rong-Yi Huang , Xiao-Ming Ren
*
*
a Anhui Key Laboratory of Functional Coordination Compounds, School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246003, China
b Department of Physical Science, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 7 July 2009
Received in revised form 31 August 2009
Accepted 1 September 2009
Available online 8 September 2009
Hydrothermal reaction of Zn(NO3)2Á6H2O with benzene-1,2,3-tricarboxylic acid (H3BTC) or 5-bromoi-
sophthalic acid (H2BIPA) in the presence of 1,4-bis(imidazol-1-ylmethyl)benzene (bix) produced two
novel coordination polymers [Zn2(OH)(BTC) (bix)]ÁH2O (1) and Zn(BIPA)(bix) (2), which were character-
ized by single-crystal X-ray diffraction, elemental analysis, IR and thermoanalysis. Complex 1 is a novel
example of the 2D (3,4)-connected nets with (42Á6)(42Á63Á8) topology. In 2, the BIPA and bix ligands linked
the Zn(II) atoms into a deeply corrugated 2D sheet. The corrugated 2D sheets polycatenate each other in a
parallel manner yielding a rare 2D ? 3D parallel polycatenation net. Thermal and luminescent properties
of two complexes have also been investigated.
Keywords:
Zinc
Polycarboxylate
Coordination polymer
Luminescence
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
ate group and the phenyl ring plane [28] have been used to bind me-
tal centers in different directions to generate many complexes with
The design and synthesis of metal–organic frameworks has be-
come a very attractive research field. The motive comes not only
from the intriguing structural diversity but also from the demand
for applications of functional materials in the fields of catalysis,
porosity, magnetism, luminescence, conductivity, sensing, nonlin-
ear optics and chirality [1–12]. Multicarboxylate ligands with
suitable spacers, especially benzene-multicarboxylato ligands are
frequent choices for metal–organic networks [13–19]. Recently,
more and more investigations have paid attention to the
coordination polymers containing asymmetric rigid benzene poly-
carboxylate acids, such as 1,2,4-benzenetricarboxylate [20], 1,2,3-
interesting magnetic and spectroscopic properties as well as a great
deal of multi-dimensional networks containing channels and cavi-
ties with various size and shapes [29,30].
Lately, a large number of MOFs based on flexible bis(imidazole)
ligands have been constructed [31–34]. Such ligands bearing alkyl
spacers are a good choice of a N-donor ligand, and to hold the ener-
getic minimum, the flexible nature of spacers allows the ligands to
bend and rotate when it coordinates to metal centers, and this of-
ten causes the structural diversity. Upon careful inspection of the
reported cases, we found that most of them are focused on the me-
tal–bis(imidazole)–inorganic counterion (such as ClÀ, ClO4À, SO4
,
2À
benzenetricarboxylate (BTC3À
)
[21]. There are at least three
NO3À) system; by contrast, the exploration of metal–bis(imidaz-
ole)–organic counterion (such as BTC3À, BIPA2À) system is less
developed [35]. With this in mind, we use H3BTC and H2BIPA as or-
ganic building blocks to obtain two new metal–organic polymers.
Herein, we report the syntheses and structures of two coordination
polymers [Zn2(OH)(BTC)(bix)]ÁH2O (1) and Zn(BIPA)(bix) (2) which
display strong blue fluorescence.
structural features of the asymmetric ligands. The ligands with high
asymmetry may result in the high asymmetric molecules or supra-
molecules. It can lead to great varieties of structures by forming
short bridges via one carboxylate end or long bridges via benzene
ring. It possesses the special orientations of the carboxylate group
to form novel framework structures, which cannot be achieved by
other carboxylate-containing ligands, such as 1,4-benzenedicarbox-
ylate [22,23], 1,3,5-benzenetricarboxylate [24,25], and 1,2,4,5-ben-
zenetetracarboxylate [26,27]. Thus, the asymmetric ligands with the
multiplicity of the dihedral angle between the plane of the carboxyl-
2. Experimental
2.1. Materials and analyses
* Corresponding authors. Tel./fax: +86 556 5500090 (G.-X. Liu).
E-mail addresses: liugx@live.com (G.-X. Liu), huangrongy@aqtc.edu.cn
(R.-Y. Huang).
All chemicals purchased were of regent grade and used without
further purification. The bix ligand was prepared according to re-
0020-1693/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2009.09.014

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G.-X. Liu et al. / Inorganica Chimica Acta 362 (2009) 5103–5108
Table 1
ported procedures [36]. Typically, the preparation of the coordina-
tion polymer was performed by combining bix with polycarboxylic
acids (benzene-1,2,3-tricarboxylic acid or 5-bromoisophthalic
acid) as the mixed coligands and transition-metal nitrate under
hydrothermal conditions in a Teflon-lined vessel (25 mL). All the
products were highly stable in air and insoluble in water and com-
mon organic solvents at ambient conditions. Elemental analyses (C,
H and N) were performed on a Vario EL III elemental analyzer.
Infrared spectra were performed on a Nicolet AVATAR-360 spec-
trophotometer with KBr pellets in the 400–4000 cmÀ1 region.
The luminescence spectra for the powdered solid samples were
measured at room temperature on a Hitachi F-4500 fluorescence
spectrophotometer with a xenon arc lamp as the light source. In
the measurements of emission and excitation spectra the pass
width is 5 nm. All the measurements were carried out under the
same experimental conditions. Thermal gravimetric analyses
(TGA) were performed on a Netzsch STA-409PC instrument in
Crystal data and structure refinement for 1 and 2.
Complex
1
2
Empirical formula
Molecular weight
Crystal system
Space group
a (Å)
C23H20N4O8Zn2
611.17
triclinic
C22H17BrN4O4Zn
546.68
monoclinic
P21/c
10.165(2)
14.368(3)
14.752(3)
90
105.276(3)
90
2078.3(7)
4
293(2)
1.747
3.143
ꢀ
P1
9.324(6)
10.059(7)
13.414(9)
83.379(11)
72.617(11)
75.142(12)
1159.4(13)
2
293(2)
1.751
2.128
620
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
T (K)
Dcalc (g cmÀ3
)
l
(mmÀ1
)
F(0 0 0)
1096
Maximum/minimum transmission
h range (°)
Reflections collected
0.8154/0.7006
2.35–25.10
5464
0.7440/0.4731
2.01–25.10
10 254
flowing N2 with a heating rate of 20 °C minÀ1
.
Independent reflections (Rint
)
3967 (0.0230)
3/334
1.039
0.0500
0.1378
3684 (0.0344)
0/289
1.092
0.0502
0.1569
2.2. Syntheses of hybrid complexes
Restraint/parameters
Goodness-of-fit (GOF) on F2
(I)]a
(I)]b
2.2.1. [Zn2(OH)(BTC)(bix)]ÁH2O (1)
R1[I > 2
wR2[I > 2
r
A
mixture containing Zn(NO3)2Á6H2O (29.6 mg, 0.1 mmol),
r
H3BTC (48.0 mg, 0.1 mmol), bix (23.8 mg, 0.1 mmol) and LiOHÁH2O
(12.3 mg, 0.3 mmol) in 15 ml deionized water was sealed in a
25 ml Teflon-lined stainless steel container and heated at 140 °C
for 3 d. Colorless block crystals of 1 were collected by filtration
and washed with water and ethanol several times with a yield of
58%. Anal. Calc. for C23H20N4O8Zn2: C, 45.20; H, 3.30; N, 9.17.
Found: C, 45.17; H, 3.37; N, 9.14%. IR(KBr, cmÀ1): 3432 (br), 3051
(w), 2923 (w), 1629 (s), 1558 (s), 1544 (s), 1521 (m), 1460 (w),
1432 (m), 1379 (s), 1361 (s), 1285 (w), 1249 (m), 1142 (w), 1119
(m), 1091 (m), 1047 (m), 958 (w), 859 (w), 834 (w), 811 (m), 769
(w), 712 (w), 683 (w), 648 (w), 628 (w), 539 (w).
a
R1
wR2 = |
=
R
||Fo| À |Fc||/
R|Fo|.
b
R
w(|Fo|2 À |Fc|2)|/
R
|w(Fo)2|1/2
.
Table 2
Selected bond lengths (Å) and angles (°) for complex 1.
Zn(1)–O(7)
1.919(4)
Zn(2)–O(4)
Zn(2)–O(7)
Zn(2)–O(2)#2
Zn(2)–N(1)
1.941(4)
1.943(4)
1.978(4)
1.997(4)
Zn(1)–N(3)#1
2.008(4)
Zn(1)–O(1)#2
2.015(4)
Zn(1)–O(6)#3
2.023(4)
Zn(1)–O(5)#3
2.358(5)
O(7)–Zn(1)–N(3)#1
O(7)–Zn(1)–O(1)#2
N(3)#1–Zn(1)–O(1)#2
O(7)–Zn(1)–O(6)#3
N(3)#1–Zn(1)–O(6)#3
O(1)#2–Zn(1)–O(6)#3
O(7)–Zn(1)–O(5)#3
N(3)#1–Zn(1)–O(5)#3
118.42(17)
96.93(15)
103.92(18)
126.88(18)
106.15(19)
99.02(16)
90.46(16)
92.52(17)
O(1)#2–Zn(1)–O(5)#3
O(6)#3–Zn(1)–O(5)#3
O(4)–Zn(2)–O(7)
O(4)–Zn(2)–O(2)#2
O(7)–Zn(2)–O(2)#2
O(4)–Zn(2)–N(1)
155.82(16)
58.84(15)
103.14(16)
119.14(17)
99.88(16)
114.01(17)
110.77(19)
108.63(18)
2.2.2. Zn(BIPA)(bix) (2)
An identical procedure with 1 was followed to prepare 2 except
H2BIPA was replaced by H3BTC. Anal. Calc. for C22H17BrN4O4Zn: C,
48.33; H, 3.13; N, 10.25. Found: C, 48.27; H, 3.17; N, 10.21%. IR data
(KBr, cmÀ1): 3419 (m), 1609 (s), 1587 (s), 1522 (m), 1475 (m), 1441
(w), 1389 (m), 1365 (s), 1321 (m), 1237 (m), 1158 (m), 1092 (m),
1055 (w), 953 (m), 836 (w), 763 (m), 725 (m), 658 (w).
O(7)–Zn(2)–N(1)
O(2)#2–Zn(2)–N(1)
Symmetry transformations used to generate equivalent atom: #1: Àx + 1, Ày + 1,
Àz; #2: Àx + 1, Ày + 2, Àz + 1; #3: Àx + 1, Ày + 1, Àz + 1.
2.3. Single-crystal X-ray diffraction
Table 3
Selected bond lengths (Å) and angles (°) for complex 2.
Single crystals of 1 and 2 were chosen for data collection on a
single X-ray diffraction. Data collection was performed on a Bruker
Zn(1)–O(1)
Zn(1)–O(4)#1
O(1)–Zn(1)–O(4)#1
O(1)–Zn(1)–N(1)
O(4)#1–Zn(1)–N(1)
1.985(3)
1.985(3)
100.17(14)
107.03(17)
108.01(16)
Zn(1)–N(1)
Zn(1)–N(3)#2
O(1)–Zn(1)–N(3)#2
O(4)#1–Zn(1)–N(3)#2
N(1)–Zn(1)–N(3)#2
2.017(4)
2.023(4)
112.21(16)
113.11(16)
115.11(17)
Smart Apex II CCD diffractometer using Mo
Ka radiation
(k = 0.71073 Å). The empirical absorption corrections were applied
[37]. The structures were solved by direct methods using the SHEL-
XS-97 program [38] and refined by full-matrix least-squares on F2
using the SHELXL-97 program [39]. All of the non-hydrogen atoms
were refined anisotropically. The hydrogen atoms of the ligands
were placed in the geometrically calculated positions. The crystal
data and structure refinement of complexes 1 and 2 are summa-
rized in Table 1. Selected bond lengths (Å) and bond angles (°)
for complexes 1 and 2 are listed in Tables 2 and 3, respectively.
Symmetry transformations used to generate equivalent atom: #1: x À 1, y, z; #2: x,
Ày + 1/2, z + 1/2.
atom is coordinated by one nitrogen atom of bix, one hydroxyl oxy-
gen atom and three carboxylate oxygen atoms from two different
BTC3À ligands in a distorted square pyramid environment, in which
the nitrogen atom occupies the apical positions and four oxygen
atoms form the basal plane. To evaluate the distortion from an
3. Results and discussion
3.1. Crystal structure descriptions
ideal square pyramid to a trigonal bipyramid, the
= 0, square pyramid; = 1, trigonal bipyramid) is normally used
[40]. The Zn1 atom has a value of 0.48. The Zn2 atom is coordi-
s parameter
(s
s
The structure of 1 contains two crystallographically indepen-
dent Zn(II) atoms, one bix ligand, one BTC ligand, one hydroxyl
group and one lattice water molecule as shown in Fig. 1. The Zn1
s
nated by one nitrogen atom of bix, one hydroxyl oxygen atom
and two carboxylate oxygen atoms of two different BTC3À ligands

G.-X. Liu et al. / Inorganica Chimica Acta 362 (2009) 5103–5108
5105
Fig. 1. Perspective view of the coordination environments of the Zn(II) atom in 1 with thermal ellipsoids at 30% probability.
Fig. 2. One-dimensional double-ribbon of 1.
Br
O
O
Zn
O
O
Zn
O
O
Zn
Zn
O
O
Zn
O
O
Zn
(b)
(a)
Scheme 1. Coordination modes of BTC3À and BIPA2À ligands.
Fig. 3. Two-dimensional network of 1.

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G.-X. Liu et al. / Inorganica Chimica Acta 362 (2009) 5103–5108
with distorted tetrahedral coordination geometry. The Zn–O/N
bond lengths are in the range of 1.919(4)–2.358(5) Å (Table 2).
The Zn1 and Zn2 atoms are bridged by a carboxylate group and a
hydroxyl group with Zn1Á Á ÁZn2 separation of 3.263(2) Å to form
a binuclear unit, which are connected through the BTC3À ligands
to generate an infinite 1D chain (Fig. 2). Each BTC3À ligand acts
10.851(6) Å. It is noteworthy that uncoordinated water molecules
in 1 occupy the vacancy between the 2D layers, hydrogen bonds
between the lattice water molecules and the carboxylate groups
of the BTC ligands stabilize the structure (Fig. S1 and Table 4).
The solvent-accessible volume is approximately 56.6 Å3 per unit
cell, and the pore volume ratio was calculated to 4.9% using the
PLATON program. Topological analysis shows that 1 is a novel exam-
ple of the 2D (3,4)-connected nets predicted by Wells [41], as illus-
trated in Fig. 4, which can be characterized by a short vertex
symbol (42Á6)(42Á63Á8) with each Zn2 core as a 4-connected node,
each BTC as a 3-connected node; the ratio of the number of 3-con-
nected to 4-connected nodes is 1:1 [42]. Usually, the (3,4)-con-
nected nets form Catalan-type or Archimedean-type 3D nets [41],
and such 2D nets with both 4- and 6-membered rings, as well as
both 3- and 4-connections, are rarely observed because the 4-con-
nected nodes generally favor the formation of 3D nets [43]. Obvi-
ously, the Zn2 node is essential to keep the planar structure
observed in 1 [44].
as a
group adopts a l2
two zinc atoms, while the other two carboxylate groups adopt a
monodentate mode and a l1
g1 chelating mode coordinating
l
4-bridge linking four zinc atoms, in which one carboxylate
-
g1
:
g1 bridging coordination mode connecting
-
g1
:
to one zinc atom, respectively (Scheme 1). The 1D chains are fur-
ther joined together by bix ligands to form a 2D layer structure
(Fig. 3). The separation of the ZnÁ Á ÁZn bridged by bix in 1 is
Table 4
Distance (Å) and angles (°) of hydrogen bonding for complex 1.
D–HÁ Á ÁA
d(D–H)
d(HÁ Á ÁA)
d(DÁ Á ÁA)
\(DHA)
Crystallographic analysis revealed that complex 2 crystallizes in
the monoclinic with space group P21/c and features a 3-fold paral-
lel interpenetrated 2D ? 3D network motif. As depicted in Fig. 5,
the asymmetric unit contains one Zn(II) ion, one BIPA molecule,
and one bix ligand. The Zn(II) ion has the distorted tetrahedral
geometry which is composed of two nitrogen atoms from the bix
ligands and two oxygen atoms from the carboxyl groups of BIPA.
Two terminal imidazole groups of the bix ligand assume trans con-
formation and have their planes steeply titled 83.92° and 73.25°
with respect to the average plane of phenyl ring. The angles of
N2–C12–C13 and N4–C19–C16 (N2 and N4 separately from the
two imidazole groups, C12 and C19 from the CH2 groups between
the phenyl ring and the imidazole ring, C13 and C16 from the phe-
nyl ring) are 114.6° and 114.7°.
O1W–H1WAÁ Á ÁO3#1
O1W–H1WBÁ Á ÁO7#2
0.85
0.85
1.93
1.97
2.784(7)
2.822(7)
178
178
Symmetry transformations used to generate equivalent atom: #1: x, À1 + y, z; #2:
1 À x, 1 À y, 1 À z.
Four Zn atoms are interlinked by the two bix and the two BIPA
ligands, thus affording a square grid with a large window of
11.24 Â 18.56 Å2, which are further connected together into a 2D
puckered 44 net (Fig. 6). The unusual topological feature of com-
plex 2 consists of the fact that the 3-fold interpenetrated sheets
are further catenated to the three adjacent (‘‘upper” and ‘‘lower”)
sheets in a parallel fashion to give an overall unique (2D ? 3D)
polycatenated network. In the resulting array (schematically illus-
trated in Figs. 7 and 8) each layer is interlocked with two others.
The type of entanglement of 2D motifs observed in complex 2 is
very rare in the area of coordination polymers.
To the best of our knowledge, only few examples of 2D ? 3D
entangled structures have been observed for polycatenating sys-
tems in parallel fashion. However, most of the studies have focused
on the 3-connected (6,3) net due to their large voids. Among the
Fig. 4. Topological (3,4)-connected 2D net in 1 (purple spheres: 4-connected Zn2
node, green spheres: 3-connected BTC node). (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 5. Coordination environment of 2 with thermal ellipsoids drawn at 30% probability and atom numbering scheme. Hydrogen atoms are omitted for clarity.

G.-X. Liu et al. / Inorganica Chimica Acta 362 (2009) 5103–5108
5107
PLATON calculation shows that the unit cell contains no residual sol-
vent-accessible void.
3.2. Thermogravimetric analyses
To characterize the thermal stabilities of the two complexes, we
carried out TGA analyses (Fig. S2). The experiments were per-
formed on samples consisting of numerous single crystals of 1
and 2 under a nitrogen atmosphere with a heating rate of 20 °C/
min. The TGA curve of 1 shows that the first weight loss of 2.99%
between 90 and 130 °C corresponds to the loss of one lattice water
molecule per formula unit (calcd. 2.95%), then it stable up to
280 °C. The framework collapsed in the temperature range 280–
800 °C before the final formation of a metal oxide. The weight of
complex 2 remains stable to ca. 320 °C, final leading to the forma-
tion of stoichiometric amount of ZnO as the residue.
Fig. 6. Top view of the (4,4) sheet in the structure of 2.
3.3. Photoluminescent properties
Coordination polymers with d10 metal centers and organic li-
gands are promising candidates for photoactive materials with po-
tential applications [52–55]. In this paper, the solid state
photoluminescent properties of complexes 1 and 2 have been
Fig. 8. Schematic view of the parallel polycatenation of the 3-fold interpenetrated
layers in 2.
Fig. 7. (a) Schematic representation of the interpenetration of the (4,4) sheets in the
structure of 2. The 4-crossing [2]-catenane motif is highlighted in green and yellow;
(b) another view of the 4-crossing [2]-catenane. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version
of this article.)
known interpenetrating (4,4) networks in coordination polymers,
the most examples are the mode of 2D ? 2D parallel interpenetra-
tion or 2D ? 3D inclined polycatenation [45–50]. However,
2D ? 3D parallel polycatenation with (4,4) nets is rarely observed,
as evidenced in a review by Batten [51]. Upon interpenetration, the
Fig. 9. Solid-state emission spectra of complexes 1 and 2.

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G.-X. Liu et al. / Inorganica Chimica Acta 362 (2009) 5103–5108
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investigated in the solid state at room temperature. As depicted in
Fig. 9, complexes 1 and 2 exhibit intense blue fluorescent emission
bands at ca. 437 and 432 nm upon excitation at ca. 330 nm. Two
emission peaks at about 450 (kex = 333 nm) and 454 nm
(kex = 349 nm) were observed for free H3BTC and H2BIPA ligands,
respectively. The emission peak of free bix ligand are located at
about 423 nm with the excitation peak at 255 nm. Taking the emis-
sion bands of these free organic ligands into consideration, the
emissions of 1 and 2 may be attributable to ligand-to-metal charge
transfer (LMCT) [56]. The enhancement of luminescence may be
attributed to ligand chelation to the metal center, which effectively
increases the rigidity of the ligand and reduces the loss of energy
by radiationless decay. Complexes 1 and 2 may be excellent candi-
dates for fluorescent materials.
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4. Conclusion
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1847.
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Mater. 14 (2002) 1879.
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In summary, we have successfully fabricated two novel coordi-
nation polymers under hydrothermal condition. Complex 1 is a no-
vel example of the 2D (3,4)-connected nets with (42Á6)(42Á63Á8)
topology, while complex 2 exhibits a rare 2D ? 3D parallel poly-
catenation net. This work will give impetus to the investigation
of the coordination chemistry of a novel asymmetric rigid aromatic
polycarboxylate acid. In addition, the emission in the blue region
indicates that complexes 1 and 2 appear to be good candidate for
a promising blue-light-emitting material.
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Acknowledgments
This work was supported by the National Natural Science Foun-
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Foundation for Outstanding Scholars of Anhui Province, China
(No. 044-J-04011), the Natural Science Foundation of Education
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