A series of transition metal coordination polymers based on a rigid bi-functional carboxylate-triazolate tecton

Article abstract of DOI:10.1039/c7ce00808b

By utilizing the pre-designed bi-functional ligand 4-{bis(4-benzoic)amino}-4H-1,2,4-triazole (H₂L), five new transition-metal-based coordination polymers, namely, {[Zn(L)]·H₂O·DMA}_n (1), {[Zn₂(L)₂]·DMF}_n (2),{[Mn(L)]·DMF}_n (3), {[Cd(L)]·DMA}_n (4) and [Cu₃(OH)₂(L)₂]_n (5) have been constructed and structurally characterized. In 1, the tetrahedral zinc ion was incorporated in the final structure. However, complexes 2, 3 and 4 bear 1D Zn-, Mn- and Cd-chains composed of metal ions, triazole and carboxyl groups, respectively. Differently, 1D [Cu₄(μ₃-OH)₂] chains had been stabilized in the 3D structure of 5. In addition, the luminescence or magnetic properties of 1-5 had been correspondingly investigated with the consideration of their crystal structure. The whole research results manifest that utilizing a bi-functional ligand containing carboxyl and triazole groups is an efficient building method in constructing functional CPs.

Full text of DOI:10.1039/c7ce00808b

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A series of transition metal coordination polymers
based on a rigid bi-functional carboxylate–
Cite this: DOI: 10.1039/c7ce00808b
triazolate tecton†
c
Nan-nan Mao,‡a Peng Hu,‡a Fan Yu,b Xi Chen,a Gui-lin Zhuang,
*
a
a
*
Tian-le Zhang
and Bao Li
By utilizing the pre-designed bi-functional ligand 4-{bisIJ4-benzoic)amino}-4H-1,2,4-triazole (H2L), five new
transition-metal-based coordination polymers, namely, {[ZnIJL)]·H2O·DMA}n (1), {[Zn2IJL)2]·DMF}n (2),{[MnIJL)]
·DMF}n (3), {[CdIJL)]·DMA}n (4) and [Cu3IJOH)2IJL)2]n (5) have been constructed and structurally characterized.
In 1, the tetrahedral zinc ion was incorporated in the final structure. However, complexes 2, 3 and 4 bear
1D Zn-, Mn- and Cd-chains composed of metal ions, triazole and carboxyl groups, respectively. Differently,
1D [Cu4IJμ3-OH)2] chains had been stabilized in the 3D structure of 5. In addition, the luminescence or
magnetic properties of 1–5 had been correspondingly investigated with the consideration of their crystal
structure. The whole research results manifest that utilizing a bi-functional ligand containing carboxyl and
triazole groups is an efficient building method in constructing functional CPs.
Received 27th April 2017,
Accepted 6th July 2017
DOI: 10.1039/c7ce00808b
rsc.li/crystengcomm
lection of the organic ligand and control of the reaction con-
ditions are key factors for achieving expected CPs. Among the
Introduction
The past two decades have witnessed the booming develop-
ment of functional coordination polymers (CPs), because of
their potential applications in the fields of gas sorption and
separation, ion-exchange, catalysis, drug delivery, photo-lumi-
nescence, magnetism, etc.1 The self-assembly of CPs depends
on the coordination habit of the metal center, the structural
character of the ligand, as well as other factors that influence
the synthesis process such as temperature, pH value of the so-
lution, and the solvent system.2 A large part of attention paid
to CPs has been done to understand the structure–activity re-
lationship, which will be propitious to the development of
structure design and oriented synthesis of the desired CPs.3
However, it is still a great challenge to synthesize CPs with
predictable structures and desired properties.4 With the con-
sideration of the synthesis conditions, tactical synthesis or se-
numerous ligands employed in CPs, versatile polycarboxylate
ligands that could assume different kinds of bridging or che-
lating modes have been extensively employed in the prepara-
tion of CPs with novel structural motifs and interesting prop-
erties.5 In comparison, CPs with N-containing ligands have to
some extent gained less interest. The syntheses of new
N-donor ligands are a long-standing fascination of chemists,
and so far, many bi-, tri-, and multidentate N-donor ligands
with or without
a N-heterocyclic backbone have been
reported.6 The 1,2,4-triazole ligand and its derivatives
presenting a hybrid of pyrazole and imidazole have been dem-
onstrated to be effective in the construction of functional CP
materials by virtue of their potential bridging patterns. The
triazole group could exhibit versatile coordination modes,
and results in variable functional materials based on the ap-
propriate connection modes and metal ions.7 With the con-
sideration of the superiority of aromatic carboxyl and triazole
ligands, the utilization of a ligand that fuses two functional
groups into one linker as a candidate in the fabrication of in-
triguing structures in the self-assembly process of CPs is
promising.8
a Key Laboratory of Material Chemistry for Energy Conversion and Storage,
School of Chemistry and Chemical Engineering, Huazhong University of Science
and Technology, Wuhan, Hubei, 430074, PR China. E-mail: libao@hust.edu.cn
b Key Laboratory of Optoelectronic Chemical Materials and Devices of Ministry of
Education, School of Chemical and Environmental Engineering, Jianghan
University, Wuhan, Hubei, 430056, PR China
c Institute of Industrial Catalysis, College of Chemical Engineering, Zhejiang
University of Technology, Zhejiang, 310023, PR China.
Herein, a rigid ligand possessing two carboxylic groups in
symmetrical positions and a N-donor triazole group, namely,
4-{bisIJ4-benzoic)amino}-4H-1,2,4-triazole (H2L), was designed
and synthesized.9 Different from other ligands possessing
three functional groups in one, for the designed ligand H2L,
the binding directions of two carboxyl groups and the triazole
group should lie in two orthogonal planes, which naturally
E-mail: glzhuang@zjut.edu.cn
† Electronic supplementary information (ESI) available: Additional computa-
tional data (PDF), X-ray crystallographic data for 1 and 2 (CIF). CCDC 1542184–
1542188. For ESI and crystallographic data in CIF or other electronic format see
DOI: 10.1039/c7ce00808b
‡ These authors contributes equally.
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satisfies a prerequisite for generation of 3D CPs with differ-
ent metal nodes under variable synthesis conditions. In this
paper, five transition metal CPs, namely, {[ZnIJL)]·H2O·DMA}n
(1), {[Zn2IJL)2]·DMF}n (2), {[MnIJL)]·DMF}n (3), {[CdIJL)]·DMA}n
(4) and [Cu3IJOH)2IJL)2]n (5), have been prepared by the hydro-
thermal method by utilizing H2L. In addition, the crystal
structures, thermal stabilities, luminescence and magnetic
properties of some of the complexes have been described in
detail. Viewed from the final structures, the two nitrogen
atoms of triazole could optionally coordinate one or two
metal ions along with the change of synthesis conditions.
Thirdly, H2O (10 ml) and EtOH (10 ml) were added to the
above product, then the reaction mixture was stirred for 24 h
at 100 °C, then cooled to room temperature and EtOH was re-
moved from the solution. Then water (50 ml) was added and
the resulting solution was filtered. Then 2M HCl was added
dropwise until the pH = 3–4, and the precipitate was filtered
and recrystallized from water to obtain the final product in
75% yield. IR (KBr, cm−1): 3447, 3117, 1669, 1597, 1383, 1274,
1180, 1061, 774. 1H-NMR (400 MHz, DMSO-d6) δ: 12.96 (s,
2H), 9.23 (s, 2H), 7.97 (d, J = 8.4 Hz, 4H), 7.07 (d, J = 8.8 Hz,
4H). MP: 266.4–272.3 °C.
Synthesis of compound 1. A mixture of ZnIJNO3)2·6H2O (16
mg, 0.054 mmol) and H2L (9.1 mg, 0.028 mmol) was
dissolved in 5 mL of DMA/EtOH/H2O (1 : 2 : 2, V/V/V). And the
reaction mixture was sonicated for 5 minutes before heating
at 85 °C in an isothermal oven for 3 days. A colorless crystal
was obtained in 62% yield. IR (KBr, cm−1): 3525, 3068, 1634,
1597, 1418, 1373, 1275, 1182, 1070, 783.
Synthesis of compound 2. A mixture of ZnIJNO3)2·6H2O (15
mg, 0.05 mmol) and H2L (8.1 mg, 0.025 mmol) was dissolved
in 4 mL of DMF/H2O (1 : 3, V/V). And the reaction mixture
was also sonicated for about 5 minutes before heating at 85
°C in an isothermal oven for 3 days. Then a colorless strip
crystal was obtained in 49% yield. IR (KBr, cm−1): 3546, 3068,
1671, 1596, 1417, 1383, 1273, 1178, 1075, 783.
Synthesis of compound 3. A mixture of MnCl2·4H2O (10
mg, 0.05 mmol) and H2L (8.1 mg, 0.025 mmol) was dissolved
in 4 mL of DMF/H2O (1 : 3, V/V). And the reaction mixture
was also sonicated for about 5 minutes before heating at 85
°C in an isothermal oven for 3 days. Then a colourless crystal
was obtained in 60% yield. IR (KBr, cm−1): 3437, 3088, 1662,
1597, 1409, 1305, 1265, 1169, 1061, 784.
Synthesis of compound 4. A mixture of H2L (0.027 mol),
CdIJNO3)2·4H2O (0.064 mmol) and HBF4 (40% aqueous, 2
drops) in a DMA/EtOH/H2O mixed solvent (DMA 2 mL; EtOH
1 mL; H2O 1 mL) was fully stirred at room temperature for 10
min, sealed in a 25 mL Teflon-lined autoclave and heated at
100 °C for 3 days. The autoclave was slowly cooled (5 °C h−1)
to ambient temperature. The resultant crystals were obtained
in 55% yield. IR (KBr, cm−1): 3439, 3096, 1615, 1548, 1394,
1305, 1263, 1182, 1060, 784.
Experimental
Materials and general methods
The organic H2L ligand (ref. 9) and other reagents for the
syntheses were of analytical grade and used as received from
commercial sources without further purification. Elemental
analyses (C, H and N) were determined on a Perkin-Elmer
2400 analyzer. The IR spectra were recorded as KBr pellets on
a Nicolet Avatar-360 spectrometer in the 4000–400 cm−1 re-
gion. Thermogravimetric analysis (TGA) was performed on a
Perkin-Elmer TG-7 analyzer heated from 25 to 800 °C under
air. The fluorescence spectra were measured on a FLS920
spectrophotometer. The magnetization and magnetic relaxa-
tion were measured by using a superconducting quantum
interference device (SQUID) magnetometer from Quantum
Design, Inc.
Synthesis of 4-{bisIJ4-benzoic)amino}-4H-1,2,4-triazole (H2L)
The ligand synthesis route was patterned after ref. 10. Firstly,
4-amino-4H-1,2,4-triazole (3.36 g, 40 mmol) was added to a
stirred suspension of potassium tert-butoxide (4.48 g, 40
mmol) in DMSO (30 mL) at 0 °C. After stirring at room tem-
perature for 2 h, a solution of 4-fluorobenzonitrile (2.44 g, 20
mmol) in DMSO (10 mL) was added dropwise below 0 °C.
The mixture was stirred for another 1.5 h at room tempera-
ture, then poured into water, and neutralized with 1 N HCl.
The precipitate was filtered and recrystallized from water to
afford the white solid, 4-((4-cyanophenyl)amino)-4H-1,2,4-
triazole. 1H-NMR (DMSO-d6): δ: 6.57 (2H, d, J = 9 Hz), 7.69
(2H, d, J = 9 Hz), 8.83 (2H, s).
Secondly, 4-((4-cyanophenyl)amino)-4H-1,2,4-triazole (2.4 g,
0.013 mmol) was added to a suspension of sodium hydride
(0.48 g) in N,N-dimethylformamide (DMF) (40 mL) with ice-
cooling. The mixture was stirred for 30 min at 40–50 °C, and
cooled to room temperature. 4-Fluorobenzonitrile (1.6 g,
0.026 mmol) was added and the reaction mixture was stirred
for 2 h at 80 °C, then cooled to room temperature. Water was
added to the resultant residue and the whole solution was
extracted with CHCl3, the organic layer was washed with wa-
ter, dried over Na2SO4 and then over vacuum. A yellow liquid
was obtained. Water was added to the yellow liquid, the solu-
tion was stirred for 5 min, and 4-{bisIJ4-cyanophenyl)amino}-4H-
1,2,4-triazole was obtained. 1H-NMR (DMSO-d6): δ: 7.04
(4H, d, J = 9 Hz), 7.69 (4H, d, J = 9 Hz) 8.44 (2H, s).
Synthesis of compound 5. A mixture of H2L (0.026 mmol)
and CuIJNO3)2·3H2O (0.028 mmol) in a DMF/CH3CN/H2O
mixed solvent (DMF 0.5 mL; CH3CN 1.5 mL; H2O 2 mL) was
fully stirred at room temperature for 10 min, sealed in a 25
mL Teflon-lined autoclave and heated at 100 °C for 3 days.
The autoclave was slowly cooled (5 °C h−1) to ambient tem-
perature. The resultant green crystals were obtained in 65%
yield. IR (KBr, cm−1): 3442, 3065, 1617, 1553, 1401, 1301,
1267, 1102, 1054, 778.
Single crystal X-ray diffraction
X-ray diffraction data of 1–2 were collected on an Oxford
Gemini S Ultra diffractometer using Mo-Kα (λ = 0.71073 Å) ra-
diation at room temperature, while the crystal structures of
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3–5 were obtained via BL17B at the Shanghai Synchrotron Ra-
diation Facility (Shanghai, China) and processed with
HKL3000.10 The structures of the complexes were solved by
direct methods, and the non-hydrogen atoms were located
from the trial structure and then refined anisotropically with
SHELXTL using a full-matrix least squares procedure based
on F2 values.11 The hydrogen atom positions were fixed geo-
metrically at calculated distances and allowed to ride on the
parent atoms. For 4, the weak diffraction intensity and corre-
sponding restrictions must be responsible for the alert A. A
summary of the structural determination and refinement for
compound 1–5 is listed in Table 1.
Scheme 1 The synthesis route of the ligand H2L.
Results and discussion
Synthesis of 1–5
gands. Two of the oxygen atoms come from the syn–syn car-
boxylates, and other one belongs to the monodentate carbox-
ylate. The coordination environment of the zinc center could
be seen as a highly distorted tetrahedral coordination geome-
try with the angles ranging from 94.23(3) to 135.53IJ4)°. The
Zn–O/N bond lengths fall in the range of 1.935(1) to 2.017(2)
Å, in accordance with the typical values of the ZnIJII) state.
Each L ligand is bound to four crystallographically different
zinc atoms utilizing its carboxylate and triazole groups, to
form a 3D coordination network (Fig. 1, down). Two coordi-
nation types of carboxylates have been observed in one li-
gand, which is bound to three zinc ions. The last zinc ion is
linked with one nitrogen atom of the triazole group. Omitting
the triazole group, a 2D layer constructed from the zinc-
carboxylate layers could be observed. Considering
4-connected zinc ions and L ligands as four-connected nodes,
a uninodal 4-connected 3D cage network with the point
(Schläfli) symbol {4·65} is topologically presented. Calculated
using the PLATON routine, the solvent accessible volume in
the dehydrated structure of 1 is about 28.8%.
The title ligand was synthesized according to the route in
Scheme 1 summarized from the related references, and the
crystalline samples were synthesized using a solvothermal
method. The syntheses of compounds 1–5 were carried out
with different metal salts and solvent systems. In the IR spec-
trum, the characteristic absorption peaks of the triazole
group and other functional ones are clearly present. The
strong absorption bands around 1586 and 1426 cm−1 are
assigned to the triazole group peaks. The strong bands
around 1600 and 1385 cm−1 are assignable to the asymmetric
and symmetric stretching vibrations of the carboxylate
groups. The absence of a band in the region of 1690–1730
cm−1 indicates complete deprotonation of the carboxylate
groups and is consistent with the results of the X-ray diffrac-
tion analysis.
Crystal structure of 1. The single-crystal X-ray analysis re-
veals that 1 crystallizes in the orthorhombic Pbca space
group, and the asymmetric unit consists of one crystallo-
graphically independent zinc atom and one L ligand (Fig. 1,
up). The Zn atom is four-coordinated by three oxygen atoms
and one nitrogen atom, which belong to the different li-
Crystal structure of 2. Compared to the structure of 1, the
different crystal structure of 2 is caused by the slight change
of reaction conditions. Single-crystal X-ray analysis reveals
Table 1 Crystal data of 1–5
1
2
3
4
5
Formula
Formula mass
Crystal system
a/Å
b/Å
c/Å
C20H21N5O6Zn
492.81
C38H34N10O10Zn2
921.53
C19H17MnN5O5
450.32
C19H17CdN5O5
434.69
C32H22Cu3N8O10
869.23
Orthorhombic
8.2270(6)
21.5096(9)
23.8825IJ11)
90
4226.2(4)
Pbca
8
Monoclinic
22.5432IJ16)
7.6652(4)
22.7737IJ11)
102.378(6)
3843.8(4)
P21/n
Orthorhombic
7.4830(15)
14.109(3)
17.972(4)
90
1897.4(7)
P212121
4
Orthorhombic
7.5850(15)
14.052(2)
18.237(4)
90
1943.8(5)
P212121
4
Monoclinic
23.508(5)
5.9780(12)
25.257(5)
99.95(3)
3496.1(13)
I2/a
β/°
Volume/Å3
Space group
Z
4
4
Rint
0.0186
0.0293
0.0737
0.0810
0.0620
CCDC no.
GOOF
1542184
1.056
1542185
1.159
1542186
1.074
1542187
1.095
1542188
1.058
Flack parameters
R1 (I > 2σ(I))
wRIJF2) (I > 2σ(I))
R1 (all data)
wRIJF2) (all data)
—
0.0350
0.0808
0.0435
—
0.0533
0.1164
0.0688
0.498(16)
0.0453
0.1229
0.0453
0.1229
0.48(2)
0.0513
0.1470
0.0516
—
0.0360
0.1009
0.0378
0.0871
0.1297
0.1487
0.1029
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Fig. 2 The perspective view of the asymmetric unit (a), a 1D Zn(2)
chain (b), a 1D Zn(1) chain (c) and the crystal packing mode (d) of 2.
Symmetric code: A, −x + 1/2, y − 1/2, −z + 1/2; B, −x + 1/2, y − 1/2, −z +
3/2; C, −x + 1/2, −y + 1/2, −z + 1/2; D, −x + 1, −y + 1, −z + 1; E, 1/2 + x,
−y + 1/2, z + 1/2; F, −x, −y + 1, −z + 1; G, x − 1/2, −y + 3/2, z − 1/2.
Fig. 1 The perspective view of an asymmetric unit (up) and the crystal
packing mode (bottom) of 1. Symmetric code: A, x, −y + 3/2, z − 1/2; B,
−x + 1, −y + 2, −z + 1; C, −x + 1/2, −y + 2, z − 1/2.
that 2 crystallizes in the monoclinic P21/n space group, and
the asymmetric unit consists of two crystallographically dif-
ferent zinc atoms and two L ligands (Fig. 2a). The Zn1 atom
is hexa-coordinated by four equatorial oxygen atoms from dif-
ferent syn–syn carboxylate groups of different ligands, and
two nitrogen atoms belonging to the triazole groups of differ-
ent ligands. The coordination environment of the zinc center
could be seen as a highly distorted octahedral coordination
geometry with the angles ranging from 82.93(2) to 110.87IJ3)°.
In contrast, the Zn2 atom adopts a tetragonal pyramid config-
uration and coordinates to three oxygen atoms and two nitro-
gen atoms. The equatorial plane of the Zn2 atom is occupied
by two oxygen atoms from two syn–syn carboxylate groups
and two nitrogen atoms of triazole groups, while the axial site
is occupied by one oxygen atom from a mono-dentate carbox-
ylate group. The Zn–O/N bond lengths fall in the range of
1.988(3) to 2.172(4) Å, in accordance with the typical values
of the ZnIJII) state. Two types of 1D zinc chains have been ob-
served in the packing structure. The adjacent Zn1 ions are
inter-connected by two syn–syn carboxylates and one bridging
triazole group of different ligands to form the 1D zinc chain,
while the adjacent Zn2 ions are inter-linked via one syn–syn
carboxylate and one bridging triazole group of different li-
gands to form the other 1D zinc chain, as shown in
Fig. 2b and c. In this way, two types of crystallographically
different ligands coordinate six or five zinc ions to form the
3D coordination network (Fig. 2d). Calculated using the
PLATON routine, the solvent accessible volume in the
dehydrated structure of 2 is about 27.0%.
Crystal structure of 3. By substituting the zinc salt with a
manganese one, a 3D Mn coordination polymer had been
synthesized. Single-crystal X-ray analysis reveals that 3 crystal-
lizes in the orthorhombic P212121 space group, and the asym-
metric unit consists of one manganese atom and one L li-
gand (Fig. 3a). The Mn1 atom is hexa-coordinated by four
equatorial oxygen atoms from different syn–syn carboxylate
groups of different ligands, and two nitrogen atoms belong-
ing to the triazole groups of different ligands. The coordina-
tion environment of the Mn center could be seen as a slightly
distorted octahedral coordination geometry with the angles
ranging from 80.18(2) to 102.65IJ3)°. The Mn–O/N bond
lengths fall in the range of 2.112(3) to 2.325(4) Å, in accor-
dance with the typical values of the MnIJII) state. The adjacent
Mn1 ions are inter-connected by two syn–syn carboxylates
and one bridging triazole group of different ligands to form
the 1D Mn chain, as shown in Fig. 3b. Each L ligand inter-
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chains had been synthesized. Single-crystal X-ray analysis re-
veals that 5 crystallizes in the monoclinic C2/c space group,
and the asymmetric unit consists of two crystallographically
different copper atoms, one hydroxyl anion and one L ligand
(Fig. 5a). The Cu1 atom is penta-coordinated with the geo-
metric parameter τ of 0.487, indicating the particular case of
a coordination environment between trigonal bipyramidal (τ
= 1) and rectangular pyramidal (τ = 0).12 The equatorial sites
are occupied by two oxygen atoms from one mono-dentate
carboxylate and one hydroxyl and one nitrogen atom of a
bridging triazole group, while the axial sites are filled with
two oxygen atoms from one syn–syn carboxylate group and
one hydroxyl. In contrast, the coordination environment of
the Cu2 center could be seen as a slightly distorted octahe-
dral configuration. The equatorial plane consists of four oxy-
gen atoms from two syn–syn carboxylate and two μ3-OH,
while the axial positions are occupied by two nitrogen atoms
from two bridging triazole. The Cu–O/N bond lengths fall in
the range of 1.905(3) to 2.371(4) Å, in accordance with the
typical values of the CuIJII) state. Two symmetric Cu1 ions are
inter-connected by two μ3-OH, which means the sharing of
one edge of two trigonal bipyramids. In addition, each μ3-OH
Fig. 3 The perspective view of an asymmetric unit (a), a 1D Mn(1)
chain (b) and the crystal packing mode (c) of 3. Symmetric code: A, x +
1/2, −y + 1/2, −z + 1; B, x, y + 1, z; C, x − 1/2, −y + 3/2, −z + 1; D, −x + 1,
y + 3/2, −z + 3/2; E, −x + 1/2, −y + 1, z + 1/2.
connected six hexa-coordinated Mn ions to form the 3D coor-
dination network (Fig. 3c). Calculated using the PLATON rou-
tine, the solvent accessible volume in the dehydrated struc-
ture of 3 is about 21.8%.
Crystal structure of 4. By reacting a cadmium ion with the
bi-functional linker, a 3D Cd coordination polymer had been
synthesized. Single-crystal X-ray analysis reveals that 4 ex-
hibits a similar crystal structure to 3, as expected from the
different bridging mode between adjacent Cd ions. The coor-
dination environment of the Cd center could be seen as a
slightly distorted pentagonal bipyramid coordination geome-
try. The axial positions are occupied by two oxygen atoms of
two syn–syn carboxylates, while the equatorial plane consisted
of two nitrogen atoms of two triazole and three oxygen atoms
of two μ2-η2:η1 carboxylate groups of two different ligands.
The adjacent Cd1 ions are inter-connected by one syn–syn
carboxylate, one bridging triazole group and one bridged oxy-
gen atom of μ2-η2:η1 carboxylate of different ligands to form
the 1D Cd chain, as shown in Fig. 4. Each L ligand inter-
connects six hepta-coordinated Cd ions to form the 3D coor-
dination network. Calculated using the PLATON routine, the
solvent accessible volume in the dehydrated structure of 4 is
about 20.7%.
Crystal structure of 5. When the bi-functional ligand
reacted with a copper ion, a different crystal structure (5)
based on the connection of ligands and 1D [Cu4IJμ3-OH)2]
Fig. 5 The perspective view of an asymmetric unit (a), the connection
mode of the ligand (b), a 1D [Cu4IJμ3-OH)2] chain (c) and the crystal
packing mode (d) of 5.
Fig. 4 The perspective view of a 1D Cd(1) chain of 4.
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still bonds one Cu2 ion to form the 1D copper-hydroxyl
chain, which is further stabilized by syn–syn carboxylate and
bridging triazole groups, as shown in Fig. 5c. This copper-
hydroxyl chain could be also seen as the duplication of
[Cu4IJμ3-OH)2] by sharing the vertex of triangles to form the
1D chain structure. Each bi-functional linker bonds to five
copper ions from three copper-hydroxyl chains to form the
3D crystal structure. Calculated using the PLATON routine,
almost no solvent accessible volume in the dehydrated struc-
ture of 5 could be observed.
be responsible for the higher thermal stability than that of 1.
The TGA curves of 3 and 4 are similar to 2, even though DMA
molecules resided in the framework. For 5, it was stable up
to 250 °C and then began to decompose. The existence of a
[Cu4IJμ3-OH)2] unit and the absence of guest solvents must be
responsible for the different thermal behavior compared to
those of 1–4.
Luminescence properties of 1–3
The compounds constructed from d10 metal centers (such as
ZnII and CdII ions) and conjugated organic linkers could be
potential candidates for photo-active materials. Therefore,
the solid-state photo luminescence behaviors of 1, 2 and 4 as
well as the free ligand were investigated in the solid state at
room temperature. The spectrum shows that the free ligand
displays an intense emission band at about 260 nm when ex-
cited at 378 nm which can be assigned to π* → n. Similar lu-
minescence properties of 1–3 could be observed to free li-
gand, indicating the absence of efficient correlation of
coordinated metal ions and deprotonated ligands.9
Comparison of different structures
By utilizing the newly designed bi-functional ligand
containing carboxyl and triazole groups and reacting with dif-
ferent transitional metal ions, five 3D CPs had been
constructed. In 1, the tetrahedral zinc ion was incorporated
in the final structure. However, complexes 2, 3 and 4 bear a
1D chain composed of metal ions, triazole and carboxyl
groups, respectively. Differently, 1D [Cu4IJμ3-OH)2] chains had
been stabilized in 3D structure of 5. Comparing the connec-
tion modes of 1 and 2, the main difference might be ascribed
to the coordination ability of the triazole group. When each
triazole binds two zinc ions via two N atoms, a 1D metal
chain could be achieved in the final structure. However, the
triazole could also exhibit the monodentate coordination
mode, which tends to result in a single-ion metal node in the
final structure. The different reaction solvent systems must
be responsible for the difference in the final structures.13 The
solvent molecules were stabilized in the final structures via
hydrogen bonding interactions, and the different steric ef-
fects of solvent molecules might disturb the coordination
modes of triazole groups. For 1, the framework interacts with
water molecules that have H-bonding interactions with DMA
molecules; for 2, the guest DMF molecules have weak interac-
tions with hydrogen atoms on triazole groups.14 For 2, 3, 4
and 5, similar 1D metal-chain structures could be observed
except for the different coordination modes of carboxyl
groups, which could be ascribed to the coordination habits
of metal ions. Overall, as observed from all the final struc-
tures, the special bent configurations of the ligand and differ-
ent weak interactions between the framework and solvent
molecules must be responsible for the construction of versa-
tile 3D CPs along with variable metal nodes.
Magnetic properties of 4 and 5
The variable-temperature magnetic susceptibilities of 3 and 5
were measured using crystalline samples under 1 KOe in the
range of 2–300 K and are shown as χMT and χM versus T plots
in Fig. 6. For 3, χMT values at 300 K are about 4.35 emu
K mol−1, close to the experimental value of the spin-only
value expected for one magnetically isolated MnII ion. Upon
cooling, the χMT values gradually decrease and then quickly
decline below 50 K, which are mainly ascribed to the total
zero-field splitting of the Mn ion or possible intramolecular
antiferromagnetic couplings. A similar magnetic behavior
was observed for 5. The χMT values at 300 K are about 1.15
emu K mol−1, lower than the experimental value of the spin-
only value (1.125 emu K mol−1 from g = 2.00) expected for
three magnetically isolated CuII ions. The data above 150 K
follow the Curie–Weiss law with C = 3.216 and 2.723 emu
K mol−1 and θ = −53.457 and −371.41 K. The above character-
istics clearly suggest overall antiferromagnetic interactions
between MnII or CuII ions in compounds 3 and 5.
Furthermore, magnetic fittings of M–T curves were
performed for the studies of the magnetic coupling mecha-
nism in 3 and 5. A glance of 3 and 5 can reveal that magnetic
properties of 5 and 3 are governed by a one-dimensional Cu4
unit-based chain and a one-dimensional single Mn-based
chain, respectively. For 5, each Cu4 unit contains three differ-
ent magnetic propagation paths: μ3-OH with ∠Cu–O–Cu =
118.77° and the NN moiety of the ligand (J1), two μ3-OH
bridges with ∠Cu–O–Cu = 96.37° (J2), and an syn–anti carbox-
ylate bridge (J3), as shown in Fig. 6 (up: insert). For 3, each
MnIJII) ion connects with adjacent ones by the bridge (J) of
syn–anti carboxylate and the NN moiety of the ligand.
Thus, the Hamiltonian operator for 5 (eqn (1)) and 3 (eqn
(2)) can be obtained as follows:
Thermal stability analyses
To further estimate the thermal stability of these complexes,
their
thermal
behaviors
were
investigated
by
thermogravimetric analyses (TGA) under a N2 atmosphere
(see Fig. S4†). For 1, the first weight loss occurred from 35 °C
to 200 °C, indicating the release of the lattice DMA mole-
cules. The weight loss was 20.2% (calc. 21.3%). The residual
framework starts to decompose beyond 325 °C. For 2, a simi-
lar thermal behavior to 1 could be observed. The residual
framework was stable up to 370 °C and then began to decom-
pose. The highly-connected 1D zinc chain structure in 2 must
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obtained best parameters are presented as follows: J1
=
−23.82 cm−1, J2 = −180.03 cm−1, J3 = 2.92 cm−1, g = 2.25, zJ =
−0.60 cm−1, TIP = 6.8 × 10−4 cm3 mol−1, R = 2.04 × 104 for 5; J
= −0.35 cm−1, D = 2.07 cm−1, g = 1.71, TIP = 5.18 × 10−4 cm3
mol−1, R = 6.44 × 10−6 for 3. For 5, the conclusions are as fol-
lows: (1) J1 of −23.82 cm−1 indicates antiferromagnetic ex-
change, contributed by a mixed bridge of μ3-OH and the
NN moiety of the ligand; (2) a larger J2 of −180.03 cm−1
shows two μ3-OH bridges induce a strong antiferromagnetic
coupling, compatible with previous simulation results in a
multinuclear cluster;17 (3) J3 of 2.92 cm−1 uncovers the ferro-
magnetic exchanges in a syn–anti carboxylate bridge, associ-
ated with poor overlap of 3d magnetic orbitals.18 For 3, a
weak antiferromagnetic coupling of J = −0.35 cm−1 shows the
synergic interaction of syn–anti carboxylate19 and the NN
moiety of the ligand. And the D value of 2.07 cm−1 is good
agreement with present results.20
(1)
(2)
A weak interaction (zJ) constant and single ion anisotropy
(D) were considered for the description of 5 and 3, respec-
tively. Concerning the huge number of one-dimensional
metal chains,15 the temperature-independent paramagnetism
(TIP) parameter was also taken into account. In this fitting,
we combined the high-efficiency searching performance of
Genetic Algorithm and the high-precision of Quantum Monte
Carlo method derived from the ALPS project16 (see the ESI†)
to search the optimal parameters. According to the principle
P
Conclusion
of the least reliability factor (R =
[(χMT)obs − (χMT)calcd]2/
P
[(χMT)obs]2), we searched the globally best parameter toward
the whole multi-dimensional space among 500 generations.
And after searching for 500 generations (see Fig. S2†), the
In summary, five new transition-metal-based CPs have been
constructed from the designed bi-functional ligand 4-{bisIJ4-
benzoic)amino}-4H-1,2,4-triazole, which exhibit diverse crystal
structures based on different metal nodes. In 1, the tetrahe-
dral zinc ion was incorporated in the final structure. How-
ever, complexes 2, 3 and 4 bear 1D chains comprised of
metal ions, triazole and carboxyl groups, respectively. Differ-
ently, 1D [Cu4IJμ3-OH)2] chains had been stabilized in 3D
structure of 5. In addition, the luminescence or magnetic
properties of 1–5 had been correspondingly investigated with
the consideration of their crystal structure. The whole re-
search results manifest that utilizing a bi-functional ligand
containing carboxyl and triazole groups is an efficient build-
ing method in constructing functional CPs. The bi-functional
ligand could bring about not only the structural diversity of
CPs, but also the variety of properties. These results will offer
more insights into the intricate structure–functionality rela-
tionship of CPs and the rational design of new crystalline
materials.
Acknowledgements
We gratefully acknowledge the National Natural Science Foun-
dation of China (21471062) and the Open Project of the State
Key Laboratory of Physical Chemistry of the Solid Surface
(Xiamen University) (201616) for financial support and the
Analytical and Testing Center, Huazhong University of Science
and Technology, for analysis and spectral measurements. We
also thank the staff from the BL17B beamline of the National
Center for Protein Sciences Shanghai (NCPSS) at the Shanghai
Synchrotron Radiation Facility for assistance during data
collection.
Notes and references
Fig. 6 Experiment plot of χmT vs. T (denoted ○) and QMC fitting (red
line) for 5 (a) and 3 (b) (inset figure is distribution sketch of CuIJII) or
MnIJII) ions).
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