Three new cpt-metal complexes displaying 0D, 1D, and 3D topology structures

Article abstract of DOI:10.1002/zaac.201000368

Three new cpt-metal complexes of different topology structures were synthesized by solvothermal methods [Hcpt = 4-(4-carboxyphenyl)-1,2,4-triazole]. The structure of [Mn(cpt)₂·2H₂O] (1) is essentially 0D monomeric, but extended into

Full text of DOI:10.1002/zaac.201000368

ARTICLE
DOI: 10.1002/zaac.201000368
Three New cpt-Metal Complexes Displaying 0D, 1D, and 3D Topology
Structures
Jiang-Feng Song,*[a] Rui-Sha Zhou,[a] Jia Zhang,[a] Chun-Yan Xu,[a] Yan-Bing Li,[a] and
Biao-Bing Wang[b]
Keywords: 4-(4-Carboxyphenyl)-1,2,4-triazole; Coordination modes; X-ray diffraction; Fluorescence; Solvothermal synthesis
Abstract. Three new cpt-metal complexes of different topology struc- nected into a 3D supramolecular network with different oriented chan-
tures were synthesized by solvothermal methods [Hcpt = 4-(4-carboxy- nels by 1D water chains. The complex [Zn(cpt)2]·0.5DMF·CH3CH2OH
phenyl)-1,2,4-triazole]. The structure of [Mn(cpt)2·2H2O] (1) is essen- (3), which crystallizes in a 3D open framework with fourfold interpen-
tially 0D monomeric, but extended into a 2D supramolecular network etrated diamondoid network topology, represents the first 3D structure
through cross-linking hydrogen bonds. In [Cu(cpt)(OH)·2H2O]·2H2O based on cpt anions. The structure differences demonstrate that the
(2), the hydroxo groups as well as cpt ligands join the copper ions into reaction metal ions have an important effect on the structures of these
an infinite polymeric [Cu(μ-cpt)(μ-OH)] chain, which is intercon- complexes.
around the C–C bond among the triazolyl ring, the benzene
Introduction
ring, and the carboxyl group will improve the coordination
The interest in metal-organic frameworks (MOF) is rapidly
modes of Hcpt ligand, and (4) a bidentate-bridging coordina-
increasing because of their intriguing structures and wide po-
tion mode similar to the 1,2,4-triazole ring results in the short
tential applications as functional materials.[1–11] Promising re-
distance of metal–metal.[19–22] Taking all these factors into con-
sults were achieved and startling applications are being devel-
sideration, we believe that Hcpt will be an ideal ligand for
oped, however, the rational design and synthesis of
constructing novel metal-organic hybrid complexes.
coordination polymers with unique structure and function still
In 2005, Guo reported the first 0D monomeric cobalt com-
remain a long-term challenge. The self-assembly process of
plex of Hcpt, in which only one nitrogen atom of triazole ring
coordination polymer is frequently influenced by various fac-
of cpt– was involved in the coordination to the cobalt atom.[23]
tors such as medium, the nature of the organic ligands, pH
Three 0D isomorphous monomeric complexes (with copper,
value of solution, temperature, the nature of metal ions, coordi-
cadmium, and cobalt) based on the ligand Hcpt were reported
nation arrangement, stereochemistry, and number of coordina-
by Lukashuk et al. in 2007, in which only the carboxylate oxy-
gen atoms of cpt– were involved in the coordination with the
metal atom.[24] Recently, three 0D isomorphous lanthanide
complexes with cubane-shaped moieties were reported, in
which a new coordination mode of cpt– was found.[25] The
aforementioned results show that investigations on the coordi-
nation chemistry of Hcpt are still in their early stages and more
systematic research is needed in order to get a better under-
standing of its coordination abilities.
tion donors provided by organic ligands.[12–18] Among them,
the nature of the organic ligand has a large impact on the build-
ing of coordination polymers with novel structures. So, it is
important to choose a suitable organic linker that can be much
more effective to design metal-organic frameworks.
The choice of 4-(4-carboxyphenyl)-1,2,4-triazole (Hcpt) is
based on following considerations: (1) the difference of the
asymmetrical coordination sites based on the carboxyl and tri-
azolyl functional group, which easily results in the formation
of different topologies, (2) a rigid backbone, which is helpful
to construct a stable metal-organic framework, (3) the rotation
The present study investigated the effect of the reaction
metal ions on the formation of different topology structures
constructed by Hcpt ligand. Herein we report the synthesis and
the crystal structures of three new coordination complexes
* Dr. J. F. Song
E-Mail: jfsong0129@gmail.com
[Mn(cpt)2·2H2O]
(1),
[Cu(cpt)(OH)·2H2O]·2H2O
(2),
[a] Department of Chemistry, College of Science
North University of China
[Zn(cpt)2]·0.5DMF·CH3CH2OH (3), as well as the reported
complex [Co(cpt)2·2H2O] (4) [Hcpt = 4-(4-carboxyphenyl)-
1,2,4-triazole and DMF = N,N-dimethylformamide]. Com-
plexes 1, 2, 3, and 4 are all obtained under solvothermal condi-
tions. Isomorphous complexes 1 and 4 both display 0D struc-
tures, however, complex 4 was already reported.[24] Complex
Taiyuan, 030051, P. R. China
[b] Shanxi Research Center of Engineering Technology for
Engineering Plastics
North University of China
Taiyuan, 030051, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201000368 or from the
author.
2+
2 displays 1D chain topology constructed by Cu(H2O)2 cati-
Z. Anorg. Allg. Chem. 2011, 637, 589–595
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
589

J.-F. Song et al.
ARTICLE
ons, OH– ions and cpt anions. Complex 3 with large cavity
exhibits fourfold interpenetrated diamondoid network topol-
ogy.
[Cu(cpt)(OH)·2H2O]·2H2O (2): The procedure was the same as that
for complex 1 except that MnCl2·4H2O was replaced by CuSO4·5H2O
(0.10 mol·L–1). Upon cooling to room temperature, the blue crystals
were filtered and washed with DMF and ethanol. Yield 70 % (based
on Hcpt). Elemental analysis: C9H15CuN3O7 (340.8): calcd. C 31.69;
H 4.40; N 12.32 %; found: C 31.75; H 4.50; N 12.37 %. IR (KBr):
Experimental Section
ν = 3460 (m), 3206 (m), 2947 (w), 1610 (s), 1527 (s), 1413 (s), 1210
˜
(s), 1005 (m), 866 (m) 788 (s), 694 (m) cm–1.
Materials and Methods
[Zn(cpt)2]·0.5DMF·CH3CH2OH (3): The procedure was the same as
that for complex 1 except that MnCl2·4H2O was replaced by
ZnCl2·4H2O (0.10 mol·L–1). Upon cooling to room temperature, the
yellow crystals were filtered and washed with DMF and ethanol. Yield
58 % (based on Hcpt). Elemental analysis: C21.50H21.50N6.50O5.50Zn
(524.32): calcd. C 49.21; H 4.10; N 14.88 %; found: C 49.25; H 4.09;
All chemicals and solvents purchased were of reagent grade and used
without further purification except Hcpt, which was prepared accord-
ing to a literature procedure.[26]
Elemental analysis (C, H, N) was performed with a Perkin–Elmer
240C elemental analyzer. IR spectra were measured with a Perkin–
Elmer Spectrum One FT–IR spectrometer using KBr pellets. Thermo-
gravimetric analyses (TGA) were performed with a Perkin–Elmer
TGA-7000 thermogravimetric analyzer under flowing air at a tempera-
ture ramp rate of 10 °C·min–1. The fluorescence spectrum of complex
3 was obtained with a LS 55 florescence/phosphorescence spectropho-
tometer at room temperature.
N 14.92 %. IR (KBr): ν = 3415 (w), 1720 (m), 1602 (s), 1510 (s),
˜
1358 (s), 1068 (m), 739 (s), 628 (m) cm–1.
[Co(cpt)2·2H2O] (4): The procedure was the same as that for complex
1 except that MnCl2·4H2O was replaced by CoCl2·6H2O (0.10
mol·L–1). Upon cooling to room temperature, the red crystals were
filtered and washed with DMF and ethanol. Yield 90 % (based on
Hcpt). Elemental analysis: C18H16CoN6O6 (471.30): calcd. C 45.83; H
3.39; N 17.82 %; found: C 45.85; H 3.45; N 17.84 %. IR (KBr): ν =
˜
Syntheses of Complexes 1–3
3276 (m), 1607 (s), 1539 (s), 1421 (s), 1098 (m), 773 (m), 507 (m)
cm–1.
[Mn(cpt)2·2H2O] (1): A solution of Hcpt (9.5 mg, 0.05 mmol) in
DMF (5 mL) containing triethylamine (28 μL, 2 mmol) was directly
mixed with a solution of MnCl2·4H2O in water (1 mL, 0.10 mol·L–1)
at room temperature in a 15 mL beaker. 3 m HNO3 was added until
Crystal Structure Determination
the mixture became clear; afterwards, ethanol (2 mL) was added. The The crystal structures were determined by single-crystal X-ray diffrac-
resulted colorless solution was transferred and sealed in a 25 mL Tef- tion. The reflection data were collected with a Bruker SMART CCD
lon-lined stainless steel reactor, and heated at 85 °C for 72 h. Upon area-detector diffractometer (Mo-Kα radiation, graphite monochroma-
cooling to room temperature, the pale pink crystals were filtered and tor) at room temperature with ω-scan mode. Empirical adsorption cor-
washed with DMF and ethanol. Yield 75 % (based on Hcpt). Elemental rection was applied to all data using SADABS program. The structure
analysis C18H16MnN6O6 (467.31): calcd C 46.22; H 3.42; N 17.98 %; was solved by direct methods and refined by full-matrix least-squares
found: C 46.28; H 3.47; N 18.04 %. IR (KBr): ν = (w = weak, m = on F2 using SHELXTL 97 software.[27] Non-hydrogen atoms were re-
˜
medium, s = strong) 3169 (m), 2944 (w), 1605 (s), 1535 (s), 1410 (s), fined anisotropically. Whenever possible, the hydrogen atoms are lo-
1253 (s), 1095 (s), 1009 (m), 891 (m), 860 (m) 790 (s), 703 (m) cm–1. cated on a difference Fourier map and refined. In other cases, the hy-
Table 1. Crystal and structure refinement data for complexes 1–3.
1
2
3
Empirical formula
Formula weight
Crystal system
Space group
a /Å
C18H16MnN6O6
467.36
C9H15CuN3O7
340.78
C21.50H21.50N6.50O5.50Zn
524.32
Monoclinic
C2/c
Monoclinic
C2/m
orthorhombic
Pbcn
13.608(3)
26.965(5)
19.7665(9)
15.8012(8)
16.9680(8)
b /Å
9.850(2)
6.7463(13)
7.1351(14)
95.80(3)
c /Å
14.434(4)
β /deg
112.529(3).
1787.1(7)
Volume /Å3
Z
1291.3(4)
5299.7(4)
4
4
8
ρcalc /g·cm–3
Absorption
Crystal size /mm
θ range /°
1.759
1.753
1.314
0.795
1.728
0.970
0.25 × 0.20 × 0.15
2.63–26.1
4876
0.28 × 0.25 × 0.15
3.11–27.47
6348
0.25 × 0.19 × 0.15
2.04–25.97
Reflections
Unique [R(int)]
Completeness
Goodness-of-fit on F2
R indexes [I > 2σ(I)]a)
R (all data)a)
27948
1787 (0.0304)
99.7 %
1602 (0.0503)
99.7 %
1.035
5201 (0.0742)
100.0 %
1.037
1.117
R1 = 0.0380, wR2 = 0.1138
R1 = 0.0538, wR2 = 0.1386
R1 = 0.0697, wR2 = 0.1520
R1 = 0.0838, wR2 = 0.2742
R1 = 0.1212, wR2 = 0.3085
R1 = 0.0527, wR2 = 0.1279
2
2
2 2 1/2.
a) R1 = Σ||Fo|–|Fc||/Σ|Fo|; wR = [Σw(Fo –Fc )2/Σw(Fo ) ]
590 www.zaac.wiley-vch.de
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Z. Anorg. Allg. Chem. 2011, 589–595

cpt-Metal Complexes Displaying 0D, 1D, and 3D Topology
Table 2. Bond lengths /Å and angles /° for complexes 1–3.
1
Mn(1)–O(1w)
2.143(2)
2.205(2)
2.224(2)
164.2(1)
92.78(6)
95.41(6)
O(1)–Mn(1)–O(1)#1
O(1w)#1–Mn(1)–O(2)
O(1w)–Mn(1)–O(2)
O(1)–Mn(1)–O(2)
O(1)#1–Mn(1)–O(2)
O(2)–Mn(1)–O(2)#1
117.66(9)
86.00(6)
86.51(6)
59.50(6)
176.72(6)
123.39(8)
Mn(1)–O(1)
Mn(1)–O(2)
O(1w)#1–Mn(1)–O(1w)
O(1w)–Mn(1)–O(1)
O(1w)–Mn(1)–O(1)#1
2
O(1w)–Cu(1)
2.576(4)
1.9324(7)
2.002(3)
180.0(3)
88.73(2)
O(2)#2–Cu(1)–N(1)
N(1)#2–Cu(1)–N(1)
O(2)–Cu(1)–O(1w)
N(1)#2–Cu(1)–O(1w)
N(1)–Cu(1)–O(1w)
91.47(2)
180.00(1)
89.98(6)
90.61(4)
89.59(4)
Cu(1)–O(2)
Cu(1)–N(1)
O(2)–Cu(1)–O(2)#2
O(2)–Cu(1)–N(1)
3
O(2)–Zn(1)
1.942(5)
1.951(6)
2.040(5)
2.014(6)
130.5(2)
O(2)–Zn(1)–N(5)
O(3)–Zn(1)–N(5)
O2–Zn(1)–N(2)
O(3)–Zn(1)–N(2)
N(5)–Zn(1)–N(2)
110.5(2)
102.8(2)
95.1(2)
112.6(2)
102.3(2)
O(3)–Zn(1)
N(2)–Zn(1)
N(5)–Zn(1)
O(2)–Zn(1)–O(3)
Symmetry transformations used to generate equivalent atoms: #1: –x, y, –z + 1/2; #2: –x + 1/2, –y + 1/2, –z + 1.
drogen atoms are geometrically fixed in complexes 1–3. The hydrogen
Results and Discussion
atoms of solvents in complexes 2 and 3 are not completely located.
Synthesis
The ethanol and disordered DMF molecules in complex 3 are located
with Dfix and Isor. All calculations were carried out using SHELXTL
97[27] and PLATON.[28] The crystallographic data and pertinent infor-
mation are summarized in Table 1. Selected bond lengths and angles
are listed in Table 2 and the geometric parameters of hydrogen bonds
are listed in Table 3.
The ligand Hcpt is insoluble in water or ethanol, however, it
is easily solved in DMF, therefore the experiments were car-
ried out under solvothermal conditions. Different metal salts
such
as
MnCl2·4H2O,
CuSO4·5H2O,
ZnCl2·4H2O,
CoCl2·6H2O, 3CdSO4·8H2O, or NiCl2·6H2O were added to
Hcpt under mixed DMF/CH3CH2OH/H2O conditions at 85 °C.
The 0D complexes containing cobalt, cadmium, or manganese
ions were easily obtained, however, the corresponding com-
plexes with higher dimensions were difficult to obtain. The
three complexes were confirmed to be isomorphous by infrared
spectroscopy (Figure S1) and single-crystal X-ray diffraction.
Moreover, the yields may depend on the amount of triethylam-
ine of reaction system, but the reaction was not significantly
affected. The highest yields were achieved when the amount
of triethylamine is 28 μL. Only unidentified green powders
were obtained when cobalt, cadmium, or manganese ions were
replaced by NiII ions. When MnCl2·4H2O was substituted by
CuSO4·5H2O or ZnCl2·4H2O, complexes 2 or 3 were obtained.
Table 3. Hydrogen bonds for complexes 1 and 2.
D–H···Aa)
d(D–H) d(H···A) d(D···A) <DHA /°
1
O1w–H1wB···N2#1 0.776
O1w–H1wA···N1#2 0.973
2
2.047
1.812
2.818
2.762
172.80
164.48
O1w–H1wA···O1#3 0.835
O1w–-H1wB···O1w#4 0.828
O2w–H2wA···O1#5 0.843
O1···O3w
2.006
2.153
2.044
2.781
2.815
2.838
2.854
2.840
153.96
136.92
156.69
O1···O2w
a) D represents “donor“ and A represents “acceptor”. Symmetry codes:
#1: –x + 1, y, –z + 1/2; #2: x – 1, –y + 1, z – 1/2; #3: x + 1/2, y + 1/
2, z; #4: –x + 1/2, –y + 1/2, –z; #5: x + 1, y + 1, z + 1.
Crystal Structures
CCDC-796490, CCDC-796491, and CCDC-796492 for complexes 1–
3, respectively, contain the supplementary crystallographic data. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif or
from the Cambridge Crystallographic Data Centre, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (Fax: +44-1223-336-033; or E-Mail:
deposit@ccdc.cam.ac.uk).
Crystal Structure of Complex 1
X-ray crystallography reveals that complex 1 with 0D topol-
ogy structure is isomorphous to the previously reported com-
plexes constructed by the first-transition metal (copper) and
cpt anions.[24] Complex 1 is composed of one MnII ion, two
deprotonated cpt anions, and two coordinated water molecules
(Figure 1a). The manganese atom with a slightly distorted oc-
tahedral arrangement, where the basal plane is occupied by
four carboxylate oxygen atoms (O1, O1a, O2, and O2a) from
Supporting Information (see footnote on the first page of this article):
IR spectra of complexes 1 and 4 as well as their isomorphous cadmium
complex.
Z. Anorg. Allg. Chem. 2011, 589–595
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591

J.-F. Song et al.
ARTICLE
two chelating cpt– ligands, lies on a crystallographic inversion corresponding bond lengths and angles are listed in Table 2,
center, and two symmetry equivalent oxygen atoms of water which further confirms the distorted octahedral arrangement of
molecules (O1w and O1wa) in axial positions forms a slightly CuII in 2. In 2, the cpt– ligand coordinates with the CuII atoms
distorted octahedral arrangement. The axial Mn–O1w bond in a μ2-N,N-bridging mode, which is reported for the first time.
length [d(Mn–O1w) = 2.143(2) Å] is slightly shorter than the
equatorial Mn–O bond lengths [d(Mn–O1) = 2.205(2) and
d(Mn–O4) = 2.224(2) Å]. The corresponding bond lengths and
angles are listed in Table 2, they further confirm the distorted
octahedral arrangement of the manganese atom. In complex 1,
the cpt– coordinates with MnII in a O,O-chelating mode, how-
ever, the nitrogen atoms of the 1,2,4-triazole groups of cpt ani-
ons are not coordinated to the metal atoms, similar to the re-
ported coordination mode of cpt–.[24]
Figure 2. View of the infinite polymeric [Cu(μ-cpt)(μ-OH)] chain in
complex 2.
The copper atoms are joined into an infinite polymeric chain
by the μ2-hydroxo groups together with μ2-cpt– along the b
axis (Figure 2). It’s noteworthy that the coordinated water mol-
ecules (O1w) are interconnected into a 1D water chain through
O–H···O hydrogen bonds (O1w–H1wb···O1w) (Figure 3). The
1D water chains and 1D Cu(OH) chains are interconnected
into a 2D puckered layer, in which another hydrogen atom
(H1wa) is outstretched and acts as hydrogen-bond donor. The
2D layers are joined into a 3D supramolecular network by
O1w–H1wa···O1 hydrogen bonds, with two kinds of different
oriented channels of dimension 12.67 × 4.46 Å2. Interestingly,
O2w and O3w reside in two kinds of different oriented chan-
nels, respectively (Figure 4).
Figure 1. (a) Coordination environment of manganese. (b) 2D supra-
molecular layer along the ac plane constructed by hydrogen bonds in
complex 1. Hydrogen atoms are omitted for clarity.
Each water molecule in complex 1 is involved in two inter-
molecular O–H···O hydrogen bonds with two uncoordinated
nitrogen atoms of the 1,2,4-triazole groups of cpt anions (N1
and N2) from two neighboring molecules to generate a 2D
supramolecular structure (Figure 1b), in which two water mol-
ecules and two triazole groups form an six-membered ring.
The π–π interactions between cpt– stabilize the 2D supramolec-
ular layer (face-to-face distance of 3.4924 Å and offset angle
of 11.33°). The corresponding hydrogen bonding parameters
are summarized in Table 3.
Crystal Structure of Complex 2
The asymmetric unit of complex 2 contains half a CuII ion,
half a μ2-cpt– anion, half a OH– ion, a coordinated water and
a lattice water molecule. Each copper atom adopts a slightly
distorted octahedral arrangement, where the basal plane is oc-
cupied by two nitrogen atoms (N1) from two symmetry equiv-
alent cpt– ligands and two oxygen atoms (O2 and O2a) from
two symmetry equivalent OH– anions, and the axial positions
are occupied by two symmetry equivalent oxygen atoms from
coordinated water molecules (O1w) (Figure 2). Due to Jahn–
Teller effect of d9 configuration, the distance of Cu–O1w (Cu–
Figure 3. View of the 2D supramolecular puckered layer constructed
by 1D water chains and 1D Cu(OH) chains in complex 2. Cpt– ions
are omitted for clarity.
According to the Cambridge Structural Database (release
O1w = 2.536 Å) is longer than the other Cu–O distances. The 5.31), we found that dozens of complexes containing the frag-
592
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Z. Anorg. Allg. Chem. 2011, 589–595

cpt-Metal Complexes Displaying 0D, 1D, and 3D Topology
Figure 5. Coordination environment of zinc in complex 3.
Figure 4. 3D supramolecular network in complex 2.
Different from complexes 1 and 2 as well as the reported
complexes based on the ligand Hcpt, cpt– adopts a new coordi-
nation mode in complex 3: μ2-N, O-bridging mode. Each ZnII
atom is connected by four cpt– bridging ligands, which consist
of two kinds of cpt–, propagating into a 3D metal-organic
framework with diamond topology (Figure 6). The intracage
Zn···Zn distances are 13.22 and 12.18 Å, which indicate a sig-
nificantly large void space of the diamondoid network. In the
crystal structure, this void space is filled by a fourfold inter-
penetration of the diamondoid network and solvent molecules
(DMF and ethanol) (Figure 6). The adamantanoid cages are
strongly compressed in the interpenetration direction along b
axis. The interpenetration mode of the four independent nets
in complex 3 is the so-called “normal” type for diamondoid
frames, which belongs to class Ia.[34–38] Interestingly, there ex-
ists in a fourfold interpenetration of the diamondoid network
in complex 3, however, very larger void space is still formed.
Calculation performed using PLATON reveals a total solvent-
accessible volume equal to 2073.6 Å3 per unit cell, which
counts for 39.1 % of the cell volume,[28] offering possibilities
of gas adsorption and gas separation, etc.
ment [Cu(μ-L)(μ-X)] were reported,[29–33] L represents substi-
tuted N-containing heterocycle molecules coordinated through
the N–N bond in a bidentate bridging manner similarly to 2,
and X is a simple bridging group such as OH, F, Cl, I, however,
to the best of our knowledge, L, which plays a crucial role in
the construction of the fragment [Cu(μ-L)(μ-X)], is not an ani-
onic organic ligand but a neutral organic molecule. So, the
fragment [Cu(cpt)(OH)] constructed by anionic N-containing
heterocycle molecules coordinated by N–N bonds in a biden-
tate bridging manner was reported for the first time. In addi-
tion, compared with the reported similar complex, [Cu(μ-L)(μ-
OH)(H2O)2]·Cl (5), the dihedral angle between the benzene
ring and the triazole ring in complex 2 is smaller than that of
complex 5 (3.01° for complex 2, and 90.00° for complex 5
[L = 4-(4-hydroxyphenyl)-1,2,4-triazole]).[29]
Crystal Structure of Complex 3
Complex 3 exhibits a 3D open framework with fourfold in-
terpenetrated diamondoid network topology and crystallizes in
space group Pbcn. The asymmetric unit of complex 3 contains
one ZnII ion, two kinds of deprotonated cpt– anions, one unco-
ordinated ethanol molecules and half a DMF molecule. Each
zinc ion adopts distorted tetrahedral arrangement and is coordi-
nated by two nitrogen atoms (N5 and N2) and two monoden-
tate carboxylate oxygen atoms (O2 and O3) from four μ2-cpt–
anions (Figure 5). The Zn–O/N bond lengths are in the range
1.942(5)–2.040(5) Å, and the corresponding O/N–Zn–O/N
bond angles range from 95.1(2)° to 130.5(2)° (Table 3), which
indicate distortion of the zinc tetrahedral arrangement. The dif-
ference in the cpt– anions is the deviation of dihedral angle
between the carboxyl plane and the benzene ring or the ben-
zene ring and the triazole ring (the dihedral angle of the car-
boxyl plane and the benzene ring is 41.34° for cpt– containing
O1, and 40.62° for the other; the dihedral angle of the benzene
ring and the triazole ring is 14.22° for cpt– containing O1, and
1.89° for the other). This difference results from the rotation
around the C–C bond among the carboxyl plane, benzene ring
and triazole ring.
Figure 6. (a) View of a single dia unit cage. (b) A single 3D dia net.
(c) Topological representation of a single 3D dia net. (d) Topological
representation of the fourfold interpenetrating network of complex 3.
TG Curves of Complexes 1–3
The thermal behaviors of complexes 1–3 were studied from
25 °C to 700 °C in air (Figure 7). The weight loss of complex
Z. Anorg. Allg. Chem. 2011, 589–595
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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J.-F. Song et al.
ARTICLE
1, which occurred at 240 °C, is assigned to the loss of coordi- upon excitation at 360 nm. Similarly, complex 3 also exhibits
nated water. The total weight loss of complex 1 amounts to blue photoluminescence with an emission maximum at 485 nm
82.34 % (calcd. 83.31 %). For complex 2, the first weight loss upon excitation at 360 nm, respectively. A comparison of the
9.73 % occurred in the range 85–142 °C and is attributed to photoluminescence spectra of Hcpt and complex 3 showed that
the loss of lattice water. The second weight loss of 65.36 % the maximum emission wavelength of complex 3 is similar to
from 142 °C to 450 °C corresponds to the loss of coordinated that of the ligand Hcpt in terms of position and band shape.
water and the decomposition of the organic component. The Therefore, the emission bands of complex 3 are mainly due to
total weight loss of complex 2 is 75.09 % (calcd. 76.67 %), an intraligand emission state similar to the reported d10 metal
whereas for complex 3, the first loss is approximately 22.57 % complexes with N-donor carboxylate ligands.[39,40] The inten-
in the range of 143–316 °C, corresponding to the weight loss sity increase of the luminescence for these complexes than
of solvent molecules (ethanol and DMF). The second weight their corresponding ligands may be attributed to the chelation
loss (58.93 %) occurred between 316 and 530 °C and is char- of the ligand to the metal atom, which increases the rigidity of
acteristic of the combustion of cpt– ligand. The total weight Hcpt and reduces the nonradiative relaxation process.
loss of complex 3 amounts to 81.50 % (calcd. 84.55 %).
Conclusions
Three new cpt-Metal complexes displaying 0D, 1D, and 3D
topologies were synthesized under solvothermal conditions.
Analyses of synthetic conditions, crystal structures and coordi-
nation modes of cpt– revealed that the reaction metal ions have
important effects on the structure of these complexes and coor-
dination modes of Hcpt ligand. This study revealed that more
new coordination polymers or porous materials with high di-
mension could be synthesized by using Hcpt. Further research
for the construction of new architectures with more transition
metals is underway in our laboratory. Complex 3 shows strong
blue photoluminescence in the solid state at room temperature.
Acknowledgement
This work was supported by the Natural Science Young Scholars Foun-
Figure 7. TGA curves of complexes 1–3.
dation of North University of China and the Scientific Research Start-
up Foundation of North University of China.
Fluorescence Spectrum of Complex 3
References
The photoluminescence spectra of complex 3 and the ligand
Hcpt in the solid state are shown in Figure 8. Hcpt exhibits
blue photoluminescence with an emission maximum at 468 nm
[1] M. Eddaoudi, D. B. Moler, H. L. Li, B. L. Chen, T. M. Reineke,
M. O’Keeffe, O. M. Yaghi, Acc. Chem. Res. 2001, s34, 319.
[2] B. J. Holliday, C. A. Mirkin, Angew. Chem. Int. Ed. 2001, 40,
2022.
[3] B. Moulton, M. J. Zaworotko, Chem. Rev. 2001, 101, 1629.
[4] O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Ed-
daoudi, J. Kim, Nature 2003, 423, 705.
[5] S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem. Int. Ed. 2004,
43, 2334.
[6] G. Ferey, Chem. Soc. Rev. 2008, 37, 191.
[7] J. R. Li, R. J. Kuppler, H. C. Zhou, Chem. Soc. Rev. 2009, 38,
1477.
[8] L. Q. Ma, C. Abney, W. B. Lin, Chem. Soc. Rev. 2009, 38, 1248.
[9] D. J. Tranchemontagne, J. L. Mendoza-Cortes, M. O’Keeffe,
O. M. Yaghi, Chem. Soc. Rev. 2009, 38, 1257.
[10] W. W. Zhou, J. T. Chen, G. Xu, M. S. Wang, J. P. Zou, X. F.
Long, G. J. Wang, G. C. Guo, J. S. Huang, Chem. Commun.
2008, 2762.
[11] M. S. Wang, G. C. Guo, W. Q. Zou, W. W. Zhou, Z. J. Zhang,
G. Xu, J. S. Huang, Angew. Chem. Int. Ed. 2008, 47, 3565.
[12] T. L. Hennigar, D. C. MacQuarrie, P. Losier, R. D. Rogers, M. J.
Zaworotko, Angew. Chem. Int. Ed. Engl. 1997, 36, 972.
[13] A. J. Blake, N. R. Brooks, N. R. Champness, P. A. Cooke, A. M.
Deveson, D. Fenske, P. Hubberstey, W. S. Li, M. Schroder, J.
Chem. Soc., Dalton Trans. 1999, 2103.
Figure 8. Solid-state emission spectra for complex 3 as well as Hcpt
ligand at room temperature.
594
www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 589–595

cpt-Metal Complexes Displaying 0D, 1D, and 3D Topology
[14] C. Y. Su, Y. P. Cai, C. L. Chen, M. D. Smith, W. Kaim, H. C. Z. [29] E. V. Lider, E. V. Peresypkina, A. I. Smolentsev, V. N. Elokhina,
Zoye, J. Am. Chem. Soc. 2003, 125, 8595.
T. I. Yaroshenko, A. V. Virovets, V. N. Ikorskii, L. G. Lavrenova,
Polyhedron 2007, 26, 1612.
[15] S. C. Chen, Z. H. Zhang, K. L. Huang, Q. Chen, M. Y. He, A. J.
Cui, C. Li, Q. Liu, M. Du, Cryst. Growth Des. 2008, 8, 3437.
[16] B. R. Manzano, F. A. Jalon, M. L. Soriano, M. C. Carrion, M. P.
Carranza, K. Mereiter, A. M. Rodriguez, A. de la Hoz, A. San-
chez-Migallon, Inorg. Chem. 2008, 47, 8957.
[30] A. B. Lysenko, E. V. Govor, K. V. Domasevitch, Inorg. Chim.
Acta 2007, 360, 55.
[31] B. Liu, G. C. Guo, J. S. Huang, J. Solid State Chem. 2006, 179,
3136.
[17] T. K. Prasad, M. V. Rajasekharan, Cryst. Growth Des. 2008, 8,
1346.
[32] Y. Wang, P. Cheng, Y. Song, D. Z. Liao, S. P. Yan, Chem. Eur. J.
2007, 13, 8131.
[18] G. J. T. Cooper, G. N. Newton, D. L. Long, P. Kogerler, M. H.
Rosnes, M. Keller, L. Cronin, Inorg. Chem. 2009, 48, 1097.
[19] J. C. Liu, G. C. Guo, J. S. Huang, X. Z. You, Inorg. Chem. 2003,
42, 235.
[33] Y. Wang, X. Q. Zhao, W. Shi, P. Cheng, D. Z. Liao, S. P. Yan,
Cryst. Growth Des. 2009, 9, 2137.
[34] I. A. Baburin, V. A. Blatov, L. Carlucci, G. Ciani, D. M. Proser-
pio, Cryst. Growth Des. 2008, 8, 519.
[20] Y. B. Lu, M. S. Wang, W. W. Zhou, G. Xu, G. C. Guo, J. S. Hu-
ang, Inorg. Chem. 2008, 47, 8935.
[35] http://www.topos.ssu.samara.ru.
[21] R. Vaidhyanathan, S. S. Iremonger, K. W. Dawson, G. K. H. Shi- [36] V. A. Blatov, L. Carlucci, G. Ciani, D. M. Proserpio, CrystEng-
mizu, Chem. Commun. 2009, 5230.
Comm 2004, 6, 378.
[37] L. Carlucci, G. Ciani, D. M. Proserpio, S. Rizzato, CrystEng-
Comm 2002, 4, 413.
[38] S. R. Batten, CrystEngComm 2001, 18, 1.
[39] S. L. Zheng, J. H. Yang, X. L. Yu, X. M. Chen, W. T. Wong,
Inorg. Chem. 2004, 43, 83.
[40] X. Li, B. L. Wu, C. Y. Niu, Y. Y. Niu, H. Y. Zhang, Cryst. Growth
Des. 2009, 9, 3423.
[22] J. P. Zhang, X. M. Chen, J. Am. Chem. Soc. 2009, 131, 5516.
[23] R. Q. Zou, L. Z. Cai, G. C. Guo, J. Mol. Struct. 2005, 737, 125.
[24] L. V. Lukashuk, A. B. Lysenko, E. B. Rusanov, A. N. Chernega,
K. V. Domasevitch, Acta Crystallogr. Sect. C 2007, 63, m140.
[25] D. Savard, P. H. Lin, T. J. Burchell, L. Korobkov, W. Werns-
dorfer, R. Clérac, M. Murugesu, Inorg. Chem. 2009, 48, 11748.
[26] R. H. Wiley, A. J. Hart, J. Org. Chem. 1953, 18, 1368.
[27] G. M. Sheldrick, SHELXS 97, Program for Crystal Structure Re-
finement, University of Göttingen: Göttingen, Germany 1998.
[28] A. L. Spek, PLATON, Molecular Geometry Program, University
of Utrecht, The Netherlands 1999.
Received: October 13, 2010
Published Online: December 27, 2010
Z. Anorg. Allg. Chem. 2011, 589–595
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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