Two 1,2,4-triazole-based zinc(II) complexes with aromatic acid as coligand: Synthesis, structure and fluorescence properties

Article abstract of DOI:10.1002/zaac.200800175

Two two-dimensional (2-D) trz-based coordination polymers, {[Zn(trz)(mb)] ·H₂O}_n (1) and {[Zn(trz)(ca)] ·H ₂O}n (2) (Htrz = 1,2,4-triazole, Hmb = 4-methylbenzoic acid, and Hca = trans-cinnamic acid), have been synthesized

Full text of DOI:10.1002/zaac.200800175

DOI: 10.1002/zaac.200800175
Two 1,2,4-Triazole-based Zinc(II) Complexes with Aromatic Acid as Coligand:
Synthesis, Structure and Fluorescence Properties
Zhong-Yi Liu, Xiu-Guang Wang, En-Cui Yang, and Xiao-Jun Zhao*
Tianjin 300387 / P. R. China, College of Chemistry & Life Science, Key Laboratory of Molecular Structure and Materials Performance,
Tianjin Normal University
Received January 21st, 2008; accepted April 28th, 2008.
Abstract. Two two-dimensional (2-D) trz-based coordination poly-
mers, {[Zn(trz)(mb)]·H2O}n (1) and {[Zn(trz)(ca)]·H2O}n (2)
(Htrz ϭ 1,2,4-triazole, Hmb ϭ 4-methylbenzoic acid, and Hca ϭ
trans-cinnamic acid), have been synthesized by diffusion method
and fully structural characterized by elemental analysis, FT-IR,
single-crystal X-ray crystallography, TG and fluorescence spectra.
Structural analysis reveals that both complexes exhibit the ana-
logous 2-D ZnII-trz layer motif with hydrophobic aromatic rings
attached on both sides despite their different crystal system and
space group (orthorhombic, Pbca for 1 and monoclinic, P21/c for
2). Interestingly, the discrete water-dimer and infinite 1-D water-
chain were observed to be entrapped in the 2-D layer of 1 and 2,
respectively, resulted from the different orientation of lattice water
molecules as well as the patterns of hydrogen bonds involved. In
addition, their similiar thermal behaviors and fluorescence emis-
sions originated from intraligand electronic transfer were also
investigated and compared.
Keywords: Zinc; Cordination polymers; 1,2,4-Triazole; Aromatic
acids; Mixed-ligands
Introduction
componets XnϪ can participate in the framework connec-
tivity as bridging ligands and are responsible for the forma-
tion of diversity substructural components together with trz
and metal ions. Such the substructure contains trinuclear
and tetranuclear clusters, adamantoid cages, chains, and
layers. More recently, aromatic/fatty acids, as one of the
functional ligands displayed by various coordination modes
of carboxylate group, are introduced into trz-based metal-
complexes as coligands by hydrothermal method and have
unexpectedly produced a series of novel 3-D topological
framework with unusual polynuclear cluster ( linear trinu-
clear, pentanuclear up to heptanuclear) as secondary build-
ing units [4]. It has been pointed out that the presence of
aromatic polycarboxylate coligand plays a significant role
in tuning the nuclearity of metal-trz clusters and the con-
nectivity of a specific network [4]. However, despite the ex-
citing preceding results, only limited trz-based complexes
with aromatic acid as coligand have been reported to date
probably resulted from the insoluble and intractable po-
lycrystalline powders during the preparation [5, 2c]. There-
fore, it is much necessary and significant to continue to sys-
tematically explore the coordination behavior involved in
aromatic acid/ trz/ metal system. Thus, in the present paper,
two novel trz-based complexes, {[Zn(trz)(mb)]·H2O}n (1)
and {[Zn(trz)(ca)]·H2O}n (2), are successfully isolated by
incorporating the aromatic acid (Hmb ϭ 4-methylbenzoic
acid, and Hca ϭ trans-cinnamic acid) as coligand under
diffusion method. The two complexes were fully structural
characterized; their thermal stability and luminescence
properties were further investigated and compared in more
detail. The structure determinations suggest that the varia-
tion of coligand from Hmb to Hca can’t significant affect
During the past decades, extensive interest has been focused
on the design and construction of coordination polymers
due to their potential applications in gas storage, separ-
ation, magnetism, nonlinear optics, luminescence, and ca-
talysis as well as their rational design principles to construct
intriguing structures and topologies [1]. Undoubtedly, the
choice of functional organic ligand with different tether
lengths, different charge balance requirements and alterna-
tive functional group orientations may play more important
roles for the overall structure and functions of the target
coordination polymers among variously possible factors in-
cluding the ligand, inorganic counterion, solvent system
and so on. In this aspect, unsubstituted 1,2,4-triazole
(Htrz), as one of small and simple five-membered hetero-
cycles, can not only function as a neutral bridging ligand
to two metal sites or in the anionic form as a bridge to the
three metal centers in μ1,2, μ2,4, and μ1,2,4 modes, but also be
potentially applied in the fields of luminescence, magnetic
materials and gas sorption [2, 3]. Recently, Zubieta and his
coworkers [3] have thoroughly investigated the structure
and properties of a series of binary metal/ triazolate and
ternary metal/ trz/ XnϪ complexes (XnϪ ϭ FϪ, ClϪ, BrϪ,
IϪ, OHϪ, NO3Ϫ SCNϪ and SO42Ϫ), indicating that anionic
* Prof. Dr. Xiao-Jun Zhao
College of Chemistry and Life Science
Tianjin Normal University
Tianjin 300387 / P. R. China
Fax: ϩ86Ϫ22Ϫ23766556
EϪmail address: xiaojun_zhao15@yahoo.com.cn
Z. Anorg. Allg. Chem. 2008, 634, 1807Ϫ1811
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1807

Z.-Y. Liu, X.-G. Wang, E.-C. Yang, X.-J. Zhao
non-hydrogen atoms. The organic hydrogen atoms were generated
geometrically. The starting positions of H attached to oxygen atom
were located in difference Fourier syntheses and then fixed geo-
metrically as riding atoms. The crystallographic data and experi-
mental details for structural analyses are summarized in Table 1.
Selected bond distances and angles for 1 and 2 are listed in Tables
2. Hydrogen bond geometries are summarized in Table 3.
CCDCϪ674930 1 and CCDCϪ674931 2 contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge via www.ccdc.can.ac.uk/conts/retrieving.html
(or from the Cambridge Crystallographic Centre, 12 Union Road,
Cambridge CB21EZ, UK; Fax: (ϩ44) 1223Ϫ336033; or
deposit@ccdc.cam.ac.uk).
their overall structure, although they belong to different
crystal system and space group. Interestingly, the orien-
tation of the lattice water molecules and their related hydro-
gen bonds arrangement lead to the presence of separate
water-dimer in 1 and infinite one-dimensional (1-D) water-
chain in 2.
Experimental Section
Reagents and instruments
All reagents were purchased commercially and used without further
purification. Doubly deionized water was used for the conventional
synthesis. Elemental analyses of carbon, hydrogen and nitrogen
were carried out with a CE-440 (Leeman-Labs) analyzer. Fourier
transform (FT) IR spectra (KBr pellets) were taken on an AVA-
TAR-370 (Nicolet) spectrometer in the range 4000 Ϫ 400 cmϪ1 re-
gion. Thermogravimetric analysis (TGA) experiments were carried
out on Shimadzu simultaneous DTG-60A compositional analysis
instrument from room temperature to 800 °C under N2 atmosphere
at a heating rate of 5 °C/min. Fluorescence spectra of the polycrys-
talline powder samples were performed on a Cary Eclipse fluor-
escence spectrophotometer (Varian) equipped with a xenon lamp
and quartz carrier at room temperature.
Table 1 Crystal data and structure refinement for 1 and 2.
1
2
Empirical formula
Formula weight
Crystal size /mm
Temperature /K
Wavelength /A
Crystal system
Space group
C10H11N3O3Zn
286.59
0.25 ϫ 0.23 ϫ 0.20 0.25 ϫ 0.23 ϫ 0.22
C11H11N3O3Zn
298.60
296(2)
296(2)
˚
0.71073
orthorhombic
Pbca
0.71073
monoclinic
P21/c
Absorption coefficient
(MoKͰ) /mmϪ1
Dc /(g/cm3)
1.871
1.815
1.451
1.463
14.6438(12)
9.6060(8)
˚
a /A
27.770(5)
9.7213(17)
9.7213(17)
90
2624.4(8)
8
˚
b /A
Synthesis of Complexes
˚
c /A
9.6475(8)
β /°
92.7480(10)
1355.54(19)
4
{[Zn(trz)(mb)]·H2O}n (1). A solution containing Hmb (6.8 mg,
0.05 mmol) and Htrz (7.2 mg, 0.1 mmol) in CH3OH (5 mL) was
carefully layered onto a buffer layer of ethyl acetate (2 mL) in a
straight glass tube, below which an aqueous solution of
Zn(OAc)2 ·2H2O (22 mg, 0.1 mmol) was placed. Upon slow evap-
oration of the mixture at room temperature, colorless block crystals
appeared on the wall of the tube within two weeks, washed with
ethanol and water and dried in air. Yield: 60 % based on Zn. Anal.
Calcd. for C10H11ZnN3O3: C, 41.91; H, 3.87; N, 14.66 %. Found:
C, 42,01; H, 4.01; N, 14.89 %. IR (KBr, cmϪ1): 3467vs, 3127w,
2364w, 1609ms, 1543ms, 1514ms, 1412ms, 1392ms, 1293m, 1200w,
1169m, 1091ms, 1039w, 1002m, 860w, 790w, 768ms, 692w, 666ms,
635m, 433w.
3
˚
V /A
Z
h/ k/ l
Ϫ33, 24 / Ϫ11, 8 /
Ϫ11, 11
1168
Ϫ11, 17 / Ϫ11, 11 /
Ϫ9, 11
608
F(000)
Reflections collected / unique
Rint
11995 / 2299
0.0298
6708 / 2397
0.0157
Completeness to theta ϭ 25.01 99.4 %
99.8 %
Data / restraints / parameters
2299 / 18 / 164
2397 / 36 / 173
0.0320 / 0.0900
0.0393 / 0.0953
1.000000 / 0.772582
1.019
a)
R1, wR2[I > 2σ (I)]
0.0624 / 0.1664
0.0690 / 0.1707
0.740 / 0.673
1.043
a)
R1, wR2(all data)
Max. and min. transmission
GOF on F2
Ϫ3)
˚
Δρmax, Δρmin (e·A
0.706 / Ϫ0.586
0.552 / Ϫ0.357
a) R1 ϭ Σ(ʈF0ΗϪΗFCʈ)/ΣΗF0Η; wR2 ϭ [Σw(ΗF0Η2ϪΗFCΗ2)2/Σw(F02)]1/2
.
{[Zn(trz)(ca)]·H2O}n (2). The colorless block single crystals of 2
suitable for X-ray analysis were obtained by adopting the similar
procedures to 1 only with Hca instead of Hmb. Yield: 52 % based
on Zn. Anal. Calcd for C11H11ZnN3O3: C, 44.25; H, 3.71; N,
14.07 %. Found: C, 44.23; H, 3.80; N, 14.14 %. IR (KBr, cmϪ1):
3454vs, 1641ms, 1555ms, 1392ms, 1296m, 1241w, 1172w, 1095m,
1004w, 975w, 876w, 774w, 724w, 664m, 604w, 486w.
Results and Discussion
Syntheses and FT-IR spectra
Due to the insoluble precipitate immediately produced by
the mixing of the reactants, 1 Ϫ 2 were finally obtained as
crystalline phases by diffusion method. It should be noted
that the preparation of the two complexes were also carried
out by hydrothermal techniques, since it is also a good
alternation for the crystallization and growth of compounds
with limited solubility. Unfortunately, the obtained results
reveals that the presence of disorder mb and ca in the corre-
sponding crystal structure. Attempts to synthesize 1 Ϫ 2 in
organic medium were failed by conventional evaporation
method. Therefore, it can be concluded that the preparation
methods greatly affect the crystallization and the growth of
the target complexes.
X-ray crystallography
Diffraction intensities for 1 Ϫ 2 were collected on Bruker APEX-
II CCD diffractometer equipped with graphite-monochromated
˚
Mo-Kα radiation with radiation wavelength 0.71073 A by using
the ϕ-ω scan technique at 296(2) K. There was no evidence of crys-
tal decay during data collection. Semiempirical absorption correc-
tions were applied (SADABS), and the program SAINT was used
for integration of the diffraction profiles [6]. The structures were
solved by direct methods and refined with the full-matrix least-
squares technique using the SHELXS-97 and SHELXL-97 pro-
grams [7]. Anisotropic thermal parameters were assigned to all
1808
www.zaac.wiley-vch.de
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 1807Ϫ1811

Two 1,2,4-Triazole-based Zinc(II) Complexes
In their IR spectra, the strong and broad adsorption
bands centered at ca. 3467 cmϪ1 for 1 and 3454 cmϪ1 for 2
are the characteristic vibration of OH group in H2O,
further confirming the existence of lattice water molecules.
The absence of the band at ca. 1700 cmϪ1 suggests the de-
protonation of aromatic acids in 1 and 2. And the asymmet-
ric (νas) and symmetric vibrations (νs) of the carboxylate
group are located at 1609 and 1392 cmϪ1 for 1, and 1641
and 1392 for 2, respectively. Their differences (217 nm for 1
and 249 nm for 2) between νas and νs, which is larger than
200 cmϪ1, indicates the unidentate coordination mode of
carboxylate group [8] and are agreement with the crystal
structure determinations. In addition, the medium bands
appeared at 1480Ϫ1520 cmϪ1 should be associated with
νCϭN of the triazole. And the bands in the 800 Ϫ 1400 cmϪ1
range are also associated with triazole ligand vibrations [9].
water molecules (see Table 3 and Figure 1c). Specially, due
to the specific orientations of the two lattices water mol-
ecules, double hydrogen bonds interactions are observed,
resulting in the presence of water-dimer.
a)
˚
Table 2 Selected bond lengths/A and angles/° for complex 1Ϫ2
1
b)
Zn(1)ϪO(1)
Zn(1)ϪN(2)
1.967(5)
2.005(5)
117.2(2)
114.8(2)
112.9(2)
Zn(1)ϪN(3)
Zn(1)ϪN(1)
2.006(5)
2.042(5)
101.0(2)
107.11(19)
101.35(19)
a)
a)
b)
O(1)ϪZn(1)ϪN(2)
O(1)ϪZn(1)ϪN(3)
O(1)ϪZn(1)ϪN(1)
N(2)aϪZn(1)ϪN(1)
N(3)bϪZn(1)ϪN(1)
N(2)aϪZn(1)ϪN(3)
b)
2
a)
Zn(1)ϪO(1)
Zn(1)ϪN(1)
O(1)ϪZn(1)ϪN(1)
O(1)ϪZn(1)ϪN(3)
N(1)ϪZn(1)ϪN(3)
1.943(3)
1.994(3)
119.44(12)
113.57(12)
111.49(11)
Zn(1)ϪN(3)
Zn(1)ϪN(2)
2.004(3)
2.031(2)
101.20(12)
107.13(10)
101.54(10)
b)
b)
O(1)ϪZn(1)ϪN(2)
N(1)ϪZn(1)ϪN(2)
a)
b)
b
N(3)aϪZn(1)ϪN(2)
a)
Structure descriptions of complexes 1 ؊ 2
a) Symmetry Codes: for 1 a Ϫx, Ϫy ϩ 1, Ϫz, b x, Ϫy ϩ 3/2, z ϩ 1/2; for 2
a Ϫx ϩ 1, y Ϫ 1/2, Ϫz ϩ 1/2, b) Ϫx ϩ 1, Ϫy, Ϫz ϩ 1.
{[Zn(trz)(mb)]·2H2O}n (1). Crystal structural determi-
nation reveals that 1 is an infinite 2-D layer constructed
from binuclear [Zn2(trz)2] subunit. The asymmetric unit
contains one Zinc(II) atom, one deprotonated trz, one mb
anion and two lattice water molecules with 50 % occupancy
for each oxygen atom. As shown in Figure 1a, the sole ZnII
atom is coordinated with three nitrogen atoms from three
different trz and one carboxylate oxygen atom from mb
anion, completing a distorted tetrahedral geometry. The
bond lengths of ZnϪN and ZnϪO are slightly varied from
a)
˚
Table 3 Selected hydrogen bond lengths/A and bond angles/°
D Ϫ H···A
d (D Ϫ H)
d (H···A)
d (D···A)
ЄDHA
1
O3 Ϫ H3A···O4a)
O4 Ϫ H4B···O3b)
O3 Ϫ H3B···O2
O4 Ϫ H4A···O2
0.850
0.850
0.851
0.857
2.564
2.397
2.518
2.506
2.920
2.921
3.023
2.770
106.41
120.38
118.90
98.88
˚
1.967(5) to 2.042(5) A, which are comparable to the pre-
viously reported values [4, 5]. In the binuclear [Zn2(trz)2]
subunit, two symmetry-related ZnII sites are bridged by two
trz anions in the N1, N2-bridging mode, forming a
{Zn2N4} heterocycle, in which the Zn···Zn separation is
2
O3 Ϫ H3A···O4a)
O3 Ϫ H3B···O4a)
O4 Ϫ H4B···O2b)
O3 Ϫ H3A···O2
0.850
0.850
0.850
0.850
2.611
2.614
2.277
2.503
2.907
3.310
2.804
3.025
101.92
140.01
120.34
120.60
˚
3.777 A and the two trz rings are strictly coplanar. Then,
the {Zn2N4} heterocycle is connected with four adjacent
subunits through the coordination bonds of ZnII atoms
with the remaining N4 position of an exocyclic trz, generat-
ing an infinite 2-D layer in bc-plane (Figure 1b). Thus, each
trz ligand affords its three nitrogen atoms to link three Zinc
sites together in μ1,2,4-tridentate mode. Viewed along the
crystallographically a-direction, the 2-D layer contains 16-
membered macrocycles composed by four Zinc sites and
four trz ligands. Topologically, this connectivity pattern
generates a 2-D 4, 82Ϫnet sheet, when both Zn1 and trz are
treated as three connected nodes. In addition, on both sides
of the wave-like layer, mb anions were further attached by
coordination of carboxy O with Zinc sites and complete
the layer motif with hydrophobic aromatic ring as exterior
(Figure 1c). Unexpectedly, the presence of mb anions can’t
lead to the significant π···π interactions between aromatic
rings within intra- and interlayer. Therefore, the adjacent
layers are interdigitatedly stacked together with no obvious
a) Symmetry Codes: for 1 a x, Ϫy ϩ 1/2, z Ϫ 1/2, b) x, Ϫy ϩ 1/2, z ϩ 1/2;
for 2 a x, y, z Ϫ 1, b x, y, z ϩ 1.
{[Zn(trz)(ca)]·H2O}n (2). Different from 1 belonging to
Pbca space group in orthorhombic crystal system, 2 crys-
tallizes in the P21/c space group of monoclinic crystal sys-
tem. However, the overall structure of 2 is much similar to
those of 1. All bond lengths around four-coordinated ZnII
site in 2 are slightly longer than those of 1 (see Table 2),
suggesting that the potentially stronger coordination ability.
Additionally, although relatively larger coligand (ca vs. mb)
was introduced in 2, the interlayer distance was shortened
˚
3.768 A obviously resulted from the much deeper interlude
between the adjacent 2-D layers. Another striking difference
between the two complexes is the orientation of lattice
water molecules, which were arranged into infinite 1-D
water-chain along the crystallographically c axis, as shown
in Figure 2b. Within 1-D water-chain, O3 solely served as
the donor of hydrogen bonds while O4 is only acts as the
acceptor. Thus, 1-D water-chain not water-dimer of 1 was
observed in 2.
˚
interactions and the interlayer Zn···Zn distance is 18.412 A
(Figure 1c). Interestingly, the separate water-dimer were
entrapped within 2-D layer by O-H···O hydrogen bonds in-
teractions between carboxylate O atom of mb and lattice
Z. Anorg. Allg. Chem. 2008, 1807Ϫ1811
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1809

Z.-Y. Liu, X.-G. Wang, E.-C. Yang, X.-J. Zhao
Figure 2 (a) Coordination environment of the Zinc(II) in 2; (b) 2-
D interdigitated layer of 2 with 1-D water-chain being trapped by
H-bonds interaction.
(expt. 29.51 % calcd. 27.13 %). Thus, the thermal behavior
of the two complexes suggests their minor difference in
thermal stability.
Figure 1 (a) Coordination environment of the Zinc(II) atom in 1;
(b) View of the Zn-trz layer along (100) direction and the 4,82-
net sheet; (c) 2-D interdigitated layers of 1 with water-dimer being
trapped by H-bonds interaction.
Thermal Stability
Thermogravimetric experiments were conducted to com-
pare the thermal stability of the two analogoue complexes.
As shown in Figure 3, the two complexes display much
similar thermal behavior. The lattice water molecules in 1
are lost between 30 °C and 95 °C (expt. 5.52 % calcd.
6.28 %). Then a region of plateau was appeared between
95 °C and 330 °C. Upon further heating, the framework
starts to collapse, accompanying the decomposition of the
mixed organic ligands (expt. 63.51 % calcd. 65.40 %), and
leave amorphous grey powder as the final products (expt.
29.18 % calcd. 28.30 %), which is calculated to be ZnO.
Compared with 1, the total release of water molecules en-
trapped in 2 was slightly quickly (expt. 5.47 % calcd.
6.02 %). And the temperature is lowered 30 °C than that of
1. In contrast, the decomposition of the 2-D layer of 2 is
slow, which began at 285 °C and ended at 580 °C (expt.
66.18 % calcd. 66.69 %). The final product is also ZnO
Figure 3 Thermogravimetric profiles for 1 Ϫ 2.
Luminescent properties
The solid-state fluorescence spectra of 1 Ϫ 2 at room tem-
perature are depicted in Figure 4 to examine the lumi-
nescent properties of the d10 metal complexes. Both com-
plexes present much similar strong emission at ca. 422 nm
and weak peaks at 510 nm upon excitation at 374 nm. To
understand the nature of the emission spectra, the lumi-
1810
www.zaac.wiley-vch.de
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 1807Ϫ1811

Two 1,2,4-Triazole-based Zinc(II) Complexes
(06YFJMJC03900, 07QTPTJC29800) and Tianjin Educational
Committee (20060501, 2006ZD07).
nescence properties of the free trz ligand under the same
conditions were also recorded for comparison. And the trz
ligand exhibit emission bands at 422 nm upon excitation at
374 nm. Therefore, the emissions of 1 Ϫ 2 may be assigned
to intraligand fluorescent emission [3, 4d]. The slight differ-
ence between the two complexes and free Htrz should be
resulted from the ligand chelation to the metal center, and
the deprotonation of the two ligands [10].
References
[1] (a) S. Kitagawa, R. Matsuda, J. Coord. Chem. Rev. 2007, 251,
2490; (b) M. Fujita, Y. J. Kwon, S. Washizu, K. Ogura, J. Am.
Chem. Soc. 1994, 116, 1151; (c) J.-R. Li, Q. Yu, E. C. Sanudo,
Y. Tao, X.-H. Bu, Chem Commun. 2007, 2602; (d) S. R. Batten,
CrystEngComm. 2001, 18, 1; (e) B. Moulton, M. Zaworotko,
J. Chem. Rev. 2001, 101, 1629; (f) A. J. Blake, N. R. Champ-
ness, P. Hubberstey, W. S. Li, M. A. Withersby, Coord. Chem.
Rev. 1999, 183, 117; (g) Y. H. Kiang, S. Lee, Z. T. Xu, W. Y.
Choe, G. B. Gardner, Adv. Mater. 2000, 12, 767; (h) O. R.
Evans, W. B. Lin, Acc. Chem. Res. 2002, 35, 511; (i) C. Janiak,
Dalton Trans. 2003, 2781; (j) G. Ferey, C. Mellot-Draznieks,
C. Serre, F. Millange, Acc. Chem. Res. 2005, 38, 217.
[2] (a) M. H. Klingale, S. Brooker, Coord. Chem. Rev. 2003, 241,
119; (b) U. Beckman, S. Brooker, Coord. Chem. Rev. 2003, 245,
17; (c) J. G. Haasnoot, Coord. Chem. Rev. 2000, 200Ϫ202, 131.
[3] (a) W. Ouellette, J. R. Galan-Mascaros, K. R. Dunbar, J. Zubi-
eta, Inorg. Chem. 2006, 45, 1909; (b) W. Ouellette, B. S. Hud-
son, J. Zubieta, Inorg. Chem. 2007, 46, 4887; (c) W. Ouellette,
M. H. Yu, C. J. O’Connor, D. Hagrman, J. Zubieta, Angew.
´
Chem. Int. Ed. 2006, 45, 3497; (d) W. Ouellette, J. R. Galan-
´
Mascaros, K. R. Dunbar, J. Zubieta, Inorg. Chem. 2006, 45,
1909.
[4] (a) H. Park, D. M. Moureau, J. B. Parise, Chem. Mater. 2006,
18, 525; (b) H. Park, J. F. Britten, U. Mueller, J. Y. Lee, J.
Li, J. B. Parise, Chem. Mater. 2007, 19, 1302; (c) H. Park, G.
Krigsfeld, J. B. Parise, Cryst. Growth Des. 2007, 7, 736; (d) Q.-
G. Zhai, C.-Z. Lu, X.-Y. Wu, S. R. Battern, Cryst. Growth
Des. 2007, 7, 2332.
Figure 4 Solid-state emission spectra of 1 Ϫ 2 at room tempera-
ture.
Conclusion
[5] W. Ouellette, B. S. Hudson, J. Zubieta, Inorg. Chem. 2007,
46, 4887.
Two ternary trz-based Zn(II) complexes with aromatic acid
as coligand were isolated by room temperature diffusion
method, which display similar Zn-trz layer motif with aro-
matic ring appending on both sides. The appearance of the
independent water-dimer in 1 and infinite 1-D water-chain
in 2 dominates their difference in structure. Additionally,
their similar thermal behaviors and fluoresce properties
were observed resulted from the analogous overall struc-
ture.
[6] SAINT; Bruker AXS: Madison, WI, 1998.
[7] (a) G. M. Sheldrick, SHELXL-97, Program for X-ray Crystal
Structure Refinement; Göttingen University: Göttingen, Ger-
many, 1997; (b) G. M. Sheldrick, SHELXS-97, Program for
X-ray Crystal Structure Solution; Göttingen University:
Göttingen, Germany, 1997.
[8] (a) G. B. Deacon, R. Phillips, J. Coord. Chem. Rev. 1980, 33,
227; (b) L. J. Bellamy, The Infrared Spectra of Complex Mol-
ecules, Wiley, New York, 1958.
[9] W. Ouellette, A. V. Prosvirin, J. Valeich, K. R. Dunbar, J. Zubi-
eta, Inorg. Chem. 2007, 46, 9067.
[10] (a) H. Yersin, A. Vogler, Photochemistry and Photophysics of
Coordination Compounds, Springer, Berlin, 1987; (b) B. Valeur,
Molecular Fluorescence: Principles and Application, Wiley-
VCH: Weinheim, 2002.
Acknowledgments. This present work was supported by the
National Natural Science Foundation of China (20571056,
20703030), the National Key Fundamental Research Project of
China (2005CCA01200), Natural Science Foundation of Tianjin
Z. Anorg. Allg. Chem. 2008, 1807Ϫ1811
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1811