Temperature-controlled solvothermal syntheses, structures and characterizations of a novel class of Zn complexes constructed from 1,4-bis[2-(5-phenyloxazolyl)]benzene

Article abstract of DOI:10.1002/ejic.200400614

Three novel complexes, ZnCl₂(H₂O)(POPOP) ·POPOP) (1), [ZnCl₂(POPOP)]_n (2), and {Zn ₂(CH₃COO)(POPOP)_1.5Cl₃}_n (3) {POPOP = 1,4-bis[2-(5-phenyloxazolyl)]benzene}, of zinc-POPOP coordination polymers have been obtained from an identical starting mixture using temperature as the only independent variable. Complexes 1-3 all crystallize in the triclinic P1 space group, but their Zn^II centers adopt different coordinations. Complex 1 consists of POPOP-coordinated zinc units and discrete POPOP molecules, 2 features an interesting zigzag chain structure, and 3 consists of unique ladder-like double-chains bridged by POPOP units. Furthermore, 1-3 display some different fluorescent emissions based on their different coordination architectures. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

Full text of DOI:10.1002/ejic.200400614

FULL PAPER
Temperature-Controlled Solvothermal Syntheses, Structures and
Characterizations of a Novel Class of Zn Complexes Constructed from
1,4-Bis[2-(5-phenyloxazolyl)]benzene
Shu-Mei Chen,[a] Can-Zhong Lu,*[a] Quan-Zheng Zhang,[a] Jiu-Hui Liu,[a] and
Xiao-Yuan Wu[a]
Keywords: Complexes / N ligands / Crystal engineering / Coordination modes / Properties
Three novel complexes, ZnCl2(H2O)(POPOP)·POPOP) (1),
[ZnCl2(POPOP)]n (2), and {Zn2(CH3COO)(POPOP)1.5Cl3}n (3)
zinc units and discrete POPOP molecules, 2 features an inter-
esting zigzag chain structure, and 3 consists of unique lad-
der-like double-chains bridged by POPOP units. Further-
more, 1−3 display some different fluorescent emissions based
on their different coordination architectures.
{POPOP
=
1,4-bis[2-(5-phenyloxazolyl)]benzene},
of
zinc−POPOP coordination polymers have been obtained from
an identical starting mixture using temperature as the only
independent variable. Complexes 1−3 all crystallize in the
triclinic P1 space group, but their ZnII centers adopt different
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
¯
coordinations. Complex 1 consists of POPOP-coordinated Germany, 2005)
Introduction
prepare new materials with interesting structural topology
and excellent physical properties, we have been particularly
Transition metal containing organic materials have at- concerned with such polymers and attempted to prepare
tracted considerable recent interest because of their poten- some materials with interesting physical properties.
tial applications in optical and electrooptical devices such
In addition, the design and synthesis of novel coordi-
as organic light-emitting diodes (OLEDs), electrochromic, nation architectures controlled by varying the reaction con-
photovoltaic and photoconductive devices, and photoref- ditions (including temperature,[18,19] metal/ligand ratio,[20]
ractive optical elements.[1Ϫ9] Polynuclear d10 metal (CuI, pH,[21] solvents,[22] and counter anions[23,24]) are of great
AgI, AuI, ZnII, or CdII) complexes have also attracted interest in coordination chemistry and reactions. Appropri-
extensive interest owing to their appealing structures and ate control of the reaction conditions makes it possible to
photoluminescent properties. A series of d10 metal organic construct new materials with useful properties. For ex-
frameworks have been described.[10,11] Some organic N-do- ample, Forster and co-workers have carried out systematic
nors such as bipyridine or related species are often chosen studies on the role of synthesis temperature as an isolated
to fabricate these various species.[12,13] Interest in the chem- reaction variable.[19] In this paper, we report the synthesis
istry of transition metalϪdiimine compounds with a conju- of three novel complexes of zincϪPOPOP coordination
gated π-system has grown rapidly because of their unique polymers, ZnCl2(H2O)(POPOP)·(POPOP) (1), [ZnCl2(PO-
physical properties. Molecular structure-property relation- POP)]n (2), and {Zn2(CH3COO)(POPOP)1.5Cl3}n (3), from
ships of organic π-conjugated materials have been identical starting materials but at different temperatures.
explored.[14Ϫ16] POPOP {POPOP
ϭ
1,4-bis[2-(5-
phenyloxazolyl)]benzene} is a long π-conjugated ligand and
often acts as a photoluminescent chromophore.[17] How-
ever, to the best of our knowledge, no studies have been
reported based on POPOP with transition metals. To
understand the coordination chemistry of POPOP and to
Results and Discussion
Synthesis and General Characterization
To design new organicϪinorganic hybrid compounds
with some multifunctional ligands, hydro(solvo)thermal
synthesis is a powerful method. At such a relatively low
temperature and under autogenous pressure, the problems
of ligand solubility and reactivity are minimized, and ap-
propriate O- and N-donor ligands can be selected by the
metal centers for efficient molecular constructions during
crystallization. Complexes 1Ϫ3 were synthesized simply un-
[a]
The State Key Laboratory of Structural Chemistry, Fujian
Institute of Research on the Structure of Matter, National
Center for Nanoscience and Nanotechnology, the Chinese
Academy of Sciences,
Fuzhou, Fujian 350002, China
Fax: (internat.) ϩ 81-591-371-4946
E-mail: czlu@fjirsm.ac.cn
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Eur. J. Inorg. Chem. 2005, 423Ϫ427
DOI: 10.1002/ejic.200400614
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
423

S.-M. Chen, C.-Z. Lu, Q.-Z. Zhang, J.-H. Liu, X.-Y. Wu
FULL PAPER
der solvothermal reaction conditions. As mentioned above, between two adjacent POPOP-coordinated zinc units in
POPOP is a long π-conjugated ligand that can offer two which ZnII atoms are located on opposite direction mutu-
N atoms for coordination. The synthesis of zincϪPOPOP ally. These three units are parallel and combine to form a
described here demonstrates that a single starting mixture basic group by obvious πϪπ interactions, with distances of
˚
can be used to obtain different zincϪPOPOP structures by 3.518(5)Ϫ3.929(6) A. A further POPOP molecule, which is
varying only the reaction temperatures. The same precur- vertical relative to the parallel layers, fills in the large cavity
sors under different reaction temperatures lead to three no- formed by the staggered arrangement of four groups.
vel complexes, 1Ϫ3, exhibiting different architectures with
different coordination fashions (Scheme 1). The coordi-
nation numbers of ZnII ions in 1Ϫ3 are the same, but their
differing topologies are a discrete arrangement, a 1D zigzag
chain arrangement, and a 1D ladder-like double-chain ar-
rangement, respectively.
Figure 2. Ball-and-stick representation of the packing diagram of 1
Scheme 1. Role of temperature in the synthesis of zincϪPOPOP
[ZnCl2(POPOP)]n (2)
complexes
A single-crystal X-ray structural analysis shows that
complex 2 has an interesting one-dimensional zigzag chain
framework, which is built up by one POPOP linked to two
Zn atoms. The zinc(ii) atom has a tetrahedral configuration
Crystal Structures of Complexes
ZnCl2(H2O)(POPOP)·(POPOP) (1)
coordinated by two chlorine atoms [Zn(1)ϪCl(1)
ϭ
The structure determination reveals that complex 1 is dis-
crete, consisting of POPOP-coordinated zinc units and PO-
POP molecules (Figure 1). The zinc(ii) atom exhibits a
˚
˚
2.2258(6) A, Zn(1)ϪCl(2) ϭ 2.2114(7) A] and two nitrogen
˚
atoms [Zn(1)ϪN(1) ϭ 2.0596(12) A, Zn(1)ϪN(2) ϭ
˚
2.0587(12) A] from two different POPOP ligands (Figure 3).
tetrahedral configuration coordinated by two chlorine
ClϪZnϪCl and NϪZnϪN bond angles are 115.15(3)° and
96.73(5)° respectively. NϪZnϪCl bond angles range from
105.96(3) to 109.56(3)°. The shortest Zn···Zn distance be-
˚
atoms [Zn(1)ϪCl(1)
ϭ
2.2238(4) A, Zn(1)ϪCl(2)
ϭ
˚
2.2124(4) A], one nitrogen atom of the POPOP ligand with
a Zn(1)ϪN(1) bond length of 2.0629(11) A, and one oxygen
atom [Zn(1)ϪOw1 ϭ 2.0193(10) A] of a water group. There
˚
˚
tween POPOP ligands is 9.184 A. Figure 4 shows that each
˚
Zn atom is coordinated by two POPOP ligands, i.e. each
POPOP ligand is connected with two zinc atoms. Based on
this coordination mode, the 1D infinite chain framework is
formed. The most interesting feature of complex 2 is that
such a coordination mode produces a unique zigzag chain
structure. The two dihedral angles between the 5-phenylox-
azolyl rings and the center benzene ring plane are 25.05°.
are three crystallographically independent POPOP ligands
with different orientations in one unit: one monodentately
coordinates to one Zn center, while the other two do not
participate in coordination and orient vertically to each
other. Interestingly, each POPOP ligand is almost co-
planar. Figure 2 shows that there is a discrete POPOP unit
Figure 1. ORTEP drawing of ZnCl2(H2O)(POPOP)·(POPOP) (1),
showing the local coordination of ZnII and atomic numbering
scheme (30% probability thermal ellipsoids)
Figure 3. ORTEP drawing of [ZnCl2(POPOP)]n (2)
424
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2005, 423Ϫ427

Novel Class of Zn Complexes Constructed from 1,4-Bis[2-(5-phenyloxazolyl)]benzene
FULL PAPER
This is presumably a consequence of the bridging nature of and coordinates to two different Zn centers. The second is
the ligands, with effective coordination to the metals being slightly distorted, with dihedral angles of 25.91°, and coor-
of primary importance.
dinates to two symmetric relative Zn centers. In other
words, each carboxyl group coordinates to two Zn atoms
and each strongly distorted POPOP ligand provides two N
atoms to coordinate with Zn atoms to form an interesting
infinite chain. In addition, the slightly distorted POPOP li-
gands bridge two adjacent chains to produce the final lad-
der-like double-chain (Figure 6).
Figure 4. (a) Zig-zag chain structure in 2; (b) space-filling plots of
the zig-zag chain
{Zn2(CH3COO)(POPOP)1.5Cl3}n (3)
X-ray crystallographic analysis reveals that complex 3
consists of an infinite ladder-like double-chain bridged by
POPOP ligands. The fundamental unit is shown in Fig-
ure 5. There are two crystallographically different Zn cen-
ters in the asymmetric unit, both displaying tetrahedral co-
ordination geometry. The Zn(1) center is defined by two
˚
chlorine
atoms
[Zn(1)ϪCl(1)
ϭ
2.2160(9)
A,
˚
Zn(1)ϪCl(2) ϭ 2.2166(10) A], one nitrogen atom from a
distorted POPOP ligand with a Zn(1)ϪN(2) bond length of
2.100(2) A, and one oxygen atom [Zn(1)ϪO(4) ϭ 2.007(2)
Figure 6. (a) 1D ladder-like double-chain structure in 3; (b) space-
filling plots of the 1D ladder-like double-chain (for clarity, only the
backbone is shown)
˚
˚
A] of a carboxylate group. NϪZn(1)ϪCl bond angles are
109.64(7)° and 109.79(7)°, and OϪZnϪCl bond angles are
106.08(7)° and 113.99(7)°, respectively. OϪZnϪN and
ClϪZnϪCl bond angles are 95.67(9)° and 119.12(4)°
respectively. The Zn(2) center is coordinated by one chlor-
The above structural descriptions show that temperature
plays a crucial role in the formation of the complexes. A
water molecule coordinates to Zn in complex 1, but no
water molecule exists in 2 or 3. However, with increasing
temperature some CH3CN solvent was hydrolyzed to form
CH3COOϪ ligands in 3. At the same time, the co-planar
POPOP ligand also becomes distorted on going from com-
plex 1 to 3. Complexes 1Ϫ3 show increasing condensation
and density at higher synthesis temperatures. Increasing
temperatures also lead to changes in topological structure
and favor higher overall dimensionality. The overall dimen-
sionality of structures 1Ϫ3 also increases Ϫ from discrete
at 100 °C, to a 1D chain at 110 °C, and a 1D double-chain
at 150 °C, respectively. The successful preparation of 1Ϫ3
reveals a clear relationship between synthesis temperature
and structure.
˚
ine atom [Zn(2)ϪCl(3) ϭ 2.2099(9) A], two nitrogen atoms
˚
˚
[Zn(2)ϪN(1) ϭ 2.047(3) A, Zn(2)ϪN(3) ϭ 2.044(2) A] from
one rather distorted POPOP ligand and one slightly dis-
torted POPOP ligand, and one oxygen atom
˚
[Zn(2)ϪO(5) ϭ 1.964(2) A] of a carboxylate group. Unlike
in 1 and 2, carboxyl groups, arising from the hydrolyzation
of CH3CN solvent, also coordinate with Zn atoms. There
are also two crystallographically different POPOP ligands
in the asymmetric unit: one is strongly distorted, with di-
hedral angles between the 5-phenyloxazolyl ring and the
center benzene ring plane of 37.64° and 9.36° respectively,
Thermogravimetric Analysis (TGA)
The stability of 2 and 3 was examined by thermogravi-
metric analysis (TGA), which revealed an onset temperature
for decomposition above 330 °C. Such stabilities make the
compounds potential candidates for practical applications.
Photoluminescence Properties
Emission spectra of complexes 1Ϫ3 in the solid state at
room temperature show intense emissions at 452 nm (λex
396 nm) for 1, 452 nm (λex ϭ 396 nm) for 2 and 460 nm
Figure 5. ORTEP drawing of {Zn2(CH3COO)(POPOP)1.5Cl3}n (3) (λex ϭ 397 nm) for 3. To understand the nature of these
ϭ
Eur. J. Inorg. Chem. 2005, 423Ϫ427
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
425

S.-M. Chen, C.-Z. Lu, Q.-Z. Zhang, J.-H. Liu, X.-Y. Wu
FULL PAPER
FLS920 TCSPC system. TGA analysises were carried under nitro-
gen with an STA449C integration thermal analyzer.
emission bands, we analyzed the photoluminescence
properties of the POPOP ligand and found that the strong-
est emission peak for POPOP is at 448 nm, which is near to
the above values. Notably, the four values do differ slightly,
which may be attributable to ligand center charge transfer.
Similar enhancements of intraligand fluorescence occur in
(polypyridyl)metal polymers.[25Ϫ26] Especially, the emission
intensity is strongest in complex 3, and its emission peak is
also slightly larger, which may be ascribed to the presence
of (CH3COO) coordinated to Zn atoms.
ZnCl2(H2O)(POPOP)·(POPOP) (1):
A mixture of POPOP
(0.036 g, 0.10 mmol), ZnCl2·4H2O (0.10 g, 0.48 mmol) and CH3CN
(10 mL) was heated in a stainless steel reactor with a Teflon liner
at 100 °C for 72 h. After cooling, within 24 h yellow crystals of 1
were obtained in 68% yield (0.030 g based on POPOP).
C48H34Cl2N4O5Zn (883.06): calcd. C 65.45, H 3.89, N 6.36; found
C 65.29, H 3.76, N 6.14. IR (KBr): ν˜ ϭ 3514 (m), 3124 (w), 1617
(m), 1594 (m), 1557 (w), 1483 (s), 1449 (w), 1416 (m), 1281 (m),
1151 (m), 1130 (w), 1025 (w), 948 (s), 849 (m), 827 (w), 762 (s), 722
(s), 688 (s), 564 (w), 492 (w) cmϪ1
.
Conclusion
[ZnCl2(POPOP)]n (2): A mixture of POPOP (0.036 g, 0.10 mmol),
ZnCl2·4H2O (0.10 g, 0.48 mmol) and CH3CN (10 mL) was heated
in a stainless steel reactor with a Teflon liner at 110 °C for 72 h.
After cooling, within 24 h yellow crystals of 2 were obtained in
65% yield (0.033 g based on POPOP). C48H32Cl4N4O4Zn2 (500.68):
calcd. C 57.83, H 3.24, N 5.62; found C 57.58, H 3.15, N 5.64. IR
(KBr): ν˜ ϭ 3454 (w), 3123 (w), 1649 (m), 1617 (m), 1595 (m), 1557
(m), 1483 (s), 1449 (w), 1416 (m), 1351 (w), 1271 (w), 1150 (s), 1130
(w), 1104 (w), 1027 (w), 981 (w), 947 (s), 868 (w), 849 (m), 829 (m),
We have successfully combined Zn metal and POPOP
{1,4-bis[2-(5-phenyloxazolyl)]benzene} to obtain three
novel zincϪPOPOP coordination polymers, ZnCl2(H2O)-
(POPOP)·(POPOP) (1), [ZnCl2(POPOP)]n (2), and
{Zn2(CH3COO)(POPOP)1.5Cl3}n (3), with different coordi-
nation architectures under solvothermal reactions. We have
also investigated the photoluminescence properties of PO-
POP with a d10 transition metal. Incorporation of ZnII
complexes into the π-electron system of a conjugated mol-
ecule revealed a clear relationship between synthesis tem-
perature and structure.
762 (s), 722 (s), 687 (s), 659 (w), 564 (w), 492 (w) cmϪ1
.
{Zn2(CH3COO)(POPOP)1.5Cl3}n (3): mixture of POPOP
A
(0.036 g, 0.10 mmol), ZnCl2·4H2O (0.10 g, 0.48 mmol) and CH3CN
(10 mL) was heated in a stainless steel reactor with a Teflon liner
at 150 °C for 72 h. After cooling, within 24 h yellow crystals of 3
were obtained in 65% yield (0.037 g based on POPOP).
C38H27Cl3N3O5Zn2 (842.72): calcd. C 54.42, H 3.25, N 5.01; found
C 54.45, H 3.20, N 5.20. IR (KBr): ν˜ ϭ 3466 (w), 3123 (w), 3090
(w), 1615 (m), 1593 (m), 1559 (s), 1480 (s), 1415 (m), 1363 (w),
1239 (w), 1149 (m), 1124 (w), 1025 (w), 947 (s), 872 (w), 850 (m),
776 (m), 765 (s), 723 (s), 689 (s), 661 (w), 610 (w), 532 (w), 495
Experimental Section
General Remarks: All syntheses were performed in poly(tetrafluoro-
ethylene)-lined stainless steel autoclaves under autogenous pressure.
Reagents were purchased commercially and were used without
further purification. Elemental analyses of C and H were per-
formed with an EA1110 CHNS-0 CE elemental analyzer. IR (KBr
pellets) spectra were recorded with a Nicolet Magna 750FT-IR
(w) cmϪ1
.
X-ray Crystallographic Study: X-ray intensities of complexes 1Ϫ3
were collected with a Bruker Smart CCD diffractometer equipped
˚
spectrometer. Fluorescent data were collected with an Edinburgh with graphite-monochromated Mo-Kα radiation (λ ϭ 0.71073 A)
Table 1. Crystallographic data for complexes 1Ϫ3
1
2
3
Empirical formula
Formula mass
Crystal size [mm]
Crystal color
C48H34Cl2N4O5Zn
883.06
0.65 ϫ 0.45 ϫ 0.25
yellow
C24H16Cl2N2O2Zn
500.68
0.40 ϫ 0.35 ϫ 0.25
yellow
C38H27Cl3N3O5Zn2
842.72
0.25 ϫ 0.20 ϫ 0.15
yellow
Crystal system
Space group
triclinic
triclinic
triclinic
¯
¯
¯
P1
P1
P1
˚
a [A]
9.8858(10)
12.8480(14)
16.8502(13)
89.927(3)
84.235(4)
69.942(5)
1999.0(3)
1.467
9.011(3)
10.790(3)
12.288(3)
64.604(6)
89.571(9)
83.515(8)
1071.3(5)
1.552
12.264
12.937
13.399
62.833(10)
69.486(13)
75.666(14)
1761.6
1.589
0.71073
2
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
Dcalcd. [g·cmϪ3
λ (Mo-Kα) [A]
]
˚
0.71073
2
0.71073
2
Z
T [K]
130.15
0.803
908
130.15
1.420
508
130.15
1.638
854
µ (Mo-Kα) [mmϪ1
F (000)
]
R1, wR2 [I Ͼ 2σ(I)]
R1, wR2 (all data)
0.0283, 0.0752
0.0307, 0.0772
0.0234, 0.0625
0.0250, 0.0641
0.0410, 0.1042
0.0464, 0.1081
426
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Novel Class of Zn Complexes Constructed from 1,4-Bis[2-(5-phenyloxazolyl)]benzene
FULL PAPER
at 130.15 K. Empirical absorption corrections were applied to the
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data using the SADABS program. Structures were solved by the
direct method and refined by full-matrix least squares on F2 using
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[3]
[4]
[5]
[6]
[7]
˚
[8]
[9]
Table 2. Selected bond lengths [A] and angles [°] for 1Ϫ3
Complex 1
[10]
[11]
[12]
[13]
[14]
Zn(1)ϪOW1
Zn(1)ϪN(1)
2.0193(10) Zn(1)ϪCl(2)
2.0629(11) Zn(1)ϪCl(1)
2.2124(4)
2.2238(4)
OW1ϪZn(1)ϪN(1) 106.57(4)
OW1ϪZn(1)ϪCl(2) 107.60(3)
N(1)ϪZn(1)ϪCl(2) 112.95(3)
OW1ϪZn(1)ϪCl(1) 108.72(4)
N(1)ϪZn(1)ϪCl(1)
Cl(2)ϪZn(1)ϪCl(1)
102.54(3)
117.871(15)
Complex 2
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Zn(1)ϪN(2)
Zn(1)ϪN(1)
N(2)ϪZn(1)ϪN(1)
N(2)ϪZn(1)ϪCl(2) 105.96(3)
N(1)ϪZn(1)ϪCl(2) 114.89(3)
2.0587(12) Zn(1)ϪCl(2)
2.0596(12) Zn(1)ϪCl(1)
2.2114(7)
2.2258(6)
113.08(3)
109.56(3)
115.15(2)
[15]
96.73(5)
N(2)ϪZn(1)ϪCl(1)
N(1)ϪZn(1)ϪCl(1)
Cl(2)ϪZn(1)ϪCl(1)
Complex 3
[16]
[17]
Zn(1)ϪO(4)
Zn(1)ϪN(2)
2.014(3)
2.103(3)
Zn(2)ϪO(5)[a]
Zn(2)ϪN(1)
1.965(2)
2.045(3)
2.046(3)
2.2101(10)
Zn(1)ϪCl(1)
Zn(1)ϪCl(2)
O(4)ϪZn(1)ϪN(2)
O(4)ϪZn(1)ϪCl(1) 106.04(7)
N(2)ϪZn(1)ϪCl(1) 109.83(8)
O(4)ϪZn(1)ϪCl(2) 113.99(7)
N(2)ϪZn(1)ϪCl(2) 109.59(8)
Cl(1)ϪZn(1)ϪCl(2) 119.14(4)
2.2154(10) Zn(2)ϪN(3)
2.2162(11) Zn(2)ϪCl(3)
[18]
[19]
[20]
M.-L. Tong, S. Kitagawa, H.-C. Changa, M. Ohbaa, J. Chem.
Soc., Chem. Commun. 2004, 418Ϫ419.
95.71(10)
O(5)[a]ϪZn(2)ϪN(1) 117.71(11)
O(5)[a] ϪZn(2)ϪN(3) 97.14(10)
´
P. M. Forster, A. R. Burbank, C. Livage, G. Fereyb, A. K.
N(1)ϪZn(2)ϪN(3)
103.10(10)
Cheetham, J. Chem. Soc., Chem. Commun. 2004, 368Ϫ369.
A. J. Blake, N. R. Brooks, N. R. Champness, P. A. Cooke, A.
M. Deveson, D. Fenske, P. Hubberstey, W.-S. Li, M. Schröder,
J. Chem. Soc., Dalton Trans. 1999, 2103Ϫ2110.
X.-X. Hu, J.-Q. Xu, P. Cheng, X.-Y. Chen, X.-B. Cui, J.-F.
Song, G.-D. Yang, T.-G. Wang, Inorg. Chem. 2004, 43,
2261Ϫ2266.
M. A. Withersby, A. J. Blake, N. R. Champness, P. A. Cooke,
P. Hubberstey, W.-S. Li, M. Schröder, Inorg. Chem. 1999, 38,
2259Ϫ2266.
J. R. Black, N. R. Champness, W. Levason, G. Reid, J. Chem.
Soc., Chem. Commun. 1995, 1277Ϫ1278.
J. R. Black, N. R. Champness, W. Levason, G. Reid, J. Chem.
Soc., Dalton Trans. 1995, 3439Ϫ3445.
O(5)[a] ϪZn(2)ϪCl(3) 114.91(8)
N(1)ϪZn(2)ϪCl(3)
N(3)ϪZn(2)ϪCl(3)
112.06(8)
109.79(8)
[21]
[22]
[a] Symmetry transformations used to generate equivalent atoms: x,
y Ϫ 1, z.
Supporting Information: The Supporting Information(see also the
footnote on the first page of this article) contains TGA analyses
for complexes 2 and 3, IR and solid-state emission spectra of the
three complexes, and the 3D packing structures of 2 and 3.
[23]
[24]
[25]
[26]
Acknowledgments
J. Zhang, Y.-R. Xie, Q. Ye, R.-G. Xiong, Z.-L. Xue, X.-Z. You,
Eur. J. Inorg. Chem. 2003, 2572Ϫ2577.
L. Han, M.-C. Hong, R.-H. Wang, J.-H. Luo, Zh.-Zh. Lin, D.-
Q. Yuan, Chem. Commun. 2003, 2580Ϫ2581.
Received July 15, 2004
This work was supported by the 973 program of the MOST
(001CB108906), the National Natural Science Foundation of China
(90206040, 20333070 and 20303021), the Natural Science Foun-
dation of Fujian Province (20002F015 and 2002J006) and the Chi-
nese Academy of Sciences.
Early View Article
Published Online November 24, 2004
Eur. J. Inorg. Chem. 2005, 423Ϫ427
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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