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Cadmium−Furandicarboxylate Coordination Polymers Prepared with
Different Types of Pyridyl Linkers: Synthesis, Divergent
Dimensionalities, and Luminescence Study
Rupam Sen,*,† Dasarath Mal,† Paula Brandaõ ,† Rute A. S. Ferreira,‡ and Zhi Lin*,†
†
Department of Chemistry, CICECO, University of Aveiro, 3810-193, Aveiro, Portugal
Department of Physics, CICECO, University of Aveiro, 3810-193, Aveiro, Portugal
‡
S Supporting Information
*
ABSTRACT: Five new metal−organic frameworks (MOFs) have been
synthesized by using cadmium ion and 2,5-furandicarboxylic acid in presence
of a variety of bridging amine ligands, [Cd(fdc)(2,2′-bpy)(H2O)]n (1),
{[Cd(fdc)(pyz)(H2O)2][Cd(fdc)](H2O)2]·H2O}n (2), {[Cd(fdc)(4,4′-bpy)(H2O)2]·EtOH}n (3), [Cd(fdc)(1,2-bpe)(H2O)]n (4), and
[{Cd2(fdc)2(H2O)4}·(1,2-bpe)]n (5), where fdc = 2,5-furandicarboxylic acid,
2,2′-bpy = 2,2′-bipyridyl, pyz = pyrazine, 4,4′-bpy = 4,4′-bipyridyl, 1,2-bpe =
1,2-di(4-pyridyl)ethylene. All the compounds were characterized by singlecrystal X-ray analysis and show diversities in their structures. Compound 1
shows linear topology propagating along the crystallographic b-axis.
Compound 2 shows supramolecular structure, where two types of 1D double chains (ladder type) are present. These chains
propagate along the crystallographic a-axis and are tightly held with each other by strong hydrogen bonds. Compound 3 reveals a
1D + 1D → 2D polycatenated MOF, where four cadmium centers form a perfect square and these squares are further linked by
the carboxylate ligand, forming a 1D tube. These tubes are interpenetrated with each other forming a polycatenated 3D MOF.
Compound 4 also possesses a polycatenated MOF, but 1D sheets are polycatenated with each other forming the 1D + 1D → 3D
MOF. Compound 5 is a 2D-based supramolecular 3D MOF, where 1,2-bpe ligands are entrapped within the layer of the 2D by
strong hydrogen bonds and π···π interaction. Luminescence of all the compounds has been investigated.
■
INTRODUCTION
A rapid expansion has been realized in the synthesis and
application of metal−organic frameworks (MOFs) during the
past decade. Immense attention on MOFs arises not only for
their fascinating capability to form a variety of architectures and
topologies but also for their potential applications such as in
catalytic reactions,1 gas adsorption and separation processes,2
and molecular magnetism3 and also as luminescent materials.4
However, it has always been a challenge to produce desired
MOF materials with controlled properties. Obtaining the
desired architectures of MOFs designed by specific organic
ligands and metal ions is a very complicated and difficult
process that depends on many parameters, such as auxiliary
ligands, pH of the medium, reaction temperature, and reactant
ratio, which have vital impact on the structure and topology of
the resulting frameworks. But a careful synthetic approach may
produce desirable MOFs with different dimensionalities and
properties.5 Moreover, molecular self-assembly processes and
isoreticular synthesis have now guided us to develop the field of
supramolecular chemistry6 and crystal engineering7 to find
novel multifunctional MOF materials. Isoreticular synthesis,
which is the classical approach to the design and assembly of
targeted MOFs, involves the linking of simple, structuredirecting geometric small units called secondary building units
(SBUs) by organic linkers into the desired framework topology.
© 2013 American Chemical Society
Isoreticular synthesis has explained the assembly process of
predesigned MOFs in a logical and straightforward manner and
the ability to tune the size and functionality of MOFs without
disturbing the overall structure. To synthesize the MOFs, the
use of molecular building blocks that have some structural
guidance toward self-assembling processes is the key issue in
this process. Recently, much effort has been devoted to the
rational design and controlled synthesis of coordination
polymers using multidentate ligands. Among the different
connecting ligands, aliphatic and aromatic carboxylic acids
(mono, di, tri, tetra, etc.) are the most deserving candidates
evolving a large class of desired MOFs. Notably, carboxylates
have versatile bridging modes; they can act as monodentate,
bidentate, and even more.8,9 Because of their variable modes of
syn−syn, syn−anti and anti−anti, they can control the topology
and the properties of the MOFs. Moreover, the bridging
carboxylate ligands can be functionalized and also postsynthetically modified quite easily. Framework materials with the
carboxylate have a wide range of variety from rigid to flexible.
One can tune the structure by introducing desired ligands
according to the demand of properties. It is worth mentioning
Received: July 9, 2013
Revised: October 14, 2013
Published: October 25, 2013
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Table 1. Crystal Data and Structure Refinement Parameters for Complexes 1−5
formula
formula wt
temp (K)
wavelength (Å)
cryst. syst.
space group
a (Å)
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
vol (Å3)
Z
calcd density (Mg/m3)
abs coeff (mm−1)
F(000)
θ range for data collection (deg)
final R indices [I > 2σ(I)]
GOF on F2
largest diff. peak and hole (e Å−3)
1
2
3
4
5
C16H12N2O6Cd
440.69
288(2)
0.71073
monoclinic
Pc
7.8256(4)
10.0204(5)
20.8235(9)
(90)
90.102(2)
(90)
1632.89(14)
4
1.793
1.373
872
2.60, −27.99
0.0251, 0.0493
1.054
0.670, −0.306
C14H16NO15Cd2
663.08
180(2)
0.71073
monoclinic
P21/n
9.9478(3)
10.9061(3)
18.6373(6)
(90)
103.2360(10)
(90)
1968.28(10)
4
2.238
2.243
1292
2.25, −33.24
0.0243, 0.0486
1.028
0.846, −0.474
C34H25N4O13Cd2
927.42
180(2)
0.71073
triclinic
P1̅
9.9344(6)
11.6032(6)
16.4640(10)
76.643(3)
82.486(3)
75.074(2)
1779.05(18)
2
1.731
1.267
924
2.40, −30.59
0.0370, 0.0754
1.098
1.338, −0.496
C30H25N3O13Cd2
860.33
180(2)
0.71073
monoclinic
P21/n
9.8908(7)
14.3305(10)
21.8335(14)
(90)
95.183(2)
(90)
3082.0(4)
4
1.854
1.454
1704
2.35, −28.35
0.0418, 0.0871
1.117
1.553, −1.663
C48H36N4O24Cd3
1390.01
150(2)
0.71073
triclinic
P1̅
10.1306(4)
10.1685(4)
11.9873(5)
83.831(2)
78.767(2)
81.005(2)
1192.51(8)
1
1.936
1.423
688
2.07, −30.63
0.0207, 0.0485
1.049
0.832, −0.407
pyrazine, 4,4′-bpy = 4,4′-bipyridyl, 1,2-bpe = 1,2-di(4-pyridyl)ethylene. Depending on the bridging ligands, we have
successfully isolated different topological frameworks, from
1D to 3D. Luminescence properties of all the compounds have
been studied and discussed.
that MOFs with large pores are of particular interest due to
their many applications from catalysis to gas adsorption. It is
well reported that bifunctional dicarboxylates served to bridge
various metal ions producing many highly porous and
catalytically active frameworks.10 Yaghi’s group has developed
a family of compounds based on one structural arrangement in
which the pore size may be tuned over a wide range. By using
longer or shorter organic molecules of similar geometry, Yaghi
et al. have now prepared 16 variations on the MOF-5 structure,
with pores varying from 3.8 to 28.8 Å in diameter.11 By tuning
the porous channel, one can rationalize the adsorption and
catalytic properties within the pores of the materials. Recently,
we have developed a series of 3D interpenetrated frameworks
by using a dicarboxylate and bridging amine ligand.12
It is noteworthy that Cd(II)-containing coordination
polymers gained much attention due to their ability to form
bonds with different donors simultaneously and the large
radius, the various coordination numbers, and the extraordinary
physical properties of the Cd(II) ion. Cadmium(II) has been
reported in tetrahedral, trigonal bipyramidal, octahedral,
distorted pentagonal bipyramidal, and distorted dodecahedral
coordination geometries.9g This structural variation in Cd2+
coordination geometry arises from two effects: (i) the large
ionic radius of Cd2+ allows flexibility in terms of coordination
number, and (ii) the d10 electronic configuration of Cd2+ ions
serves to eliminate ligand field effects and thereby permits
diverse geometries. To date, researchers have reported a
number of frameworks with different dimensionalities. Cd(II)
coordination polymers are now highly desired for their
prospective applications in catalysis, luminescent materials,
NLO materials, phase transformation, and host−guest chemistry.9g−i In continuation of our work, herein we introduce a
series of cadmium-based furandicarboxylate frameworks using
different bridging amine ligands, [Cd(fdc)(2,2′-bpy)(H2O)]n
(1), {[Cd(fdc)(pyz)(H2O)2][Cd(fdc)](H2O)2]·H2O}n (2),
{[Cd(fdc)(4,4′-bpy)(H2O)2]·EtOH}n (3), [Cd(fdc)(1,2-bpe)(H2O)]n (4), and [{Cd2(fdc)2(H2O)4}·(1,2-bpe)]n (5), where
fdc = 2,5-furandicarboxylic acid, 2,2′-bpy = 2,2′-bipyridyl, pyz =
■
EXPERIMENTAL SECTION
Materials and Physical Measurements. Cadmium nitrate
hexahydrate, fdc, pyz, 4,4′-bpy, 1,2-bpe, and 2,2′-bpy were purchased
from Aldrich and were used as received. Fourier transformed infrared
spectra of samples suspended in KBr pellets were measured on a
Unican Mattson Mod 7000 spectrophotometer equipped with a
DTGS CsI detector. Elemental analyses (CHN) were performed using
a Perkin−Elmer 240 elemental analyzer. Thermogravimetric analyses
(TGA) were carried out using a Shimadzu TGA 50, with a heating rate
of 5 °C/min, under a continuous stream of nitrogen with a flow rate of
20 cm3/min. The powder X-ray diffraction (PXRD) patterns of the
samples were recorded with a Philips X’Pert MPD diffractometer
equipped with an X’Celerator detector. The photoluminescence
spectra were recorded at room temperature with a modular double
grating excitation spectrofluorimeter with a TRIAX 320 emission
monochromator (Fluorolog-3, Horiba Scientific) coupled to an R928
Hamamatsu photomultiplier, using a front face acquisition mode. The
excitation source was a 450 W Xe arc lamp. The emission spectra were
corrected for detection and optical spectral response of the
spectrofluorimeter, and the excitation spectra were corrected for the
spectral distribution of the lamp intensity using a photodiode reference
detector.
X-ray Crystallography. Single crystal X-ray diffraction data of 1−
5 were collected on a Bruker SMART APEX CCD X-ray
diffractometer using graphite-monochromated Mo Kα radiation (λ =
0.71073 Å). The determination of integrated intensities and cell
refinement were performed with the SAINT13 software package using
a narrow-frame integration algorithm. An empirical absorption
correction (SADABS)14 was applied. All the structures were solved
by direct methods and refined using the full-matrix least-squares
technique against F2 with anisotropic displacement parameters for
non-hydrogen atoms with the programs SHELXS97 and
SHELXL97.15 The hydrogen atoms of the C−H bonds were placed
at geometrical positions and refined with Uiso = 1.2Ueq of the atom to
which they are attached, whereas the hydrogen atoms bonded to water
molecules were obtained from the last final difference Fourier maps
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Article
Table 2. Selected Bond Lengths [Å] and Angles [deg] for Complexes 1−5
bond distances
CdA−O1A
CdA−O11A
CdA−O2A
CdA−O3A
CdA−O12A
CdA−N13A
CdA−N24A
CdB−O1B
CdB−O3B
CdB−O12B
CdB−O2B
CdB−N13B
CdB−N24B
Cd1−O1
Cd1−O2
Cd1−O4
Cd1−O12
Cd1−O13
Cd1−N14
Cd2−O17
Cd2−O18
Cd2−O19
Cd2−O20
Cd2−O28
Cd2−O29
Cd1−O1
Cd1−O2
Cd1−O3
Cd1−O11
Cd1−O12
bond angles
Compound 1
2.287(3)
O1A−CdA−O11A
2.300(2)
O1A−CdA−O2A
2.356(2)
O11A−CdA−O2A
2.460(2)
O1A−CdA−N13A
2.566(2)
O11A−CdA−N13A
2.381(3)
O1A−CdA−N24A
2.324(3)
O2A−CdA−N13A
2.294(2)
O1A−CdA−O3A
2.299(2)
N13A−CdA−O3A
2.356(2)
O1A−CdA−O12A
2.566(2)
O11A−CdA−O12A
2.385(2)
N24A−CdA−O12A
2.316(3)
O2A−CdA−O12A
Compound 2
2.2487(13)
O1−Cd1−O2
2.2617(14)
O1−Cd1−O4
2.2683(12)
O2−Cd1−O4
2.4100(12)
O1−Cd1−N14
2.4009(13)
O2−Cd1−N14
2.3973(15)
O4−Cd1−N14
2.2941(14)
O1−Cd1−O13
2.2530(15)
O2−Cd1−O13
2.4304(13)
O4−Cd1−O13
2.3591(12)
O18−Cd2−O29
2.2834(13)
O18−Cd2−O17
2.2784(14)
O17−Cd2−O20
Compound 3
2.312(2)
O1−Cd1−O2
2.3810(19)
O1−Cd1−O3
2.4312(19)
O1−Cd1−O12
2.2991(18)
O2−Cd1−O12
2.5164(19)
O3−Cd1−O12
bond distances
96.65(9)
92.65(9)
87.74(7)
164.67(9)
98.68(9)
100.84(10)
88.04(9)
84.00(8)
83.93(9)
78.75(8)
53.44(7)
77.37(8)
138.11(7)
Cd2−O13
Cd2−O24
Cd2−O15
Cd2−N34
Cd2−N37
Cd1−O1
Cd1−O2
Cd1−O3
Cd1−O4
Cd1−O12
Cd1−O13
Cd2−O14
Cd2−O15
Cd2−O16
Cd1−N26
Cd2−N37
Cd2−N40
80.98(5)
137.70(5)
88.26(5)
96.36(5)
177.24(5)
94.23(5)
136.19(5)
89.66(5)
84.02(5)
90.38(6)
170.54(6)
87.91(5)
Cd1−O1
Cd1−O2
Cd1−O3
Cd2−O4
Cd2−O12
Cd2−O13
Cd2−O14
Cd2−O23
Cd2−O24
C8−C9
C9−C10
O3−C5
93.24(7)
91.28(7)
92.03(7)
136.84(6)
167.70(6)
bond angles
Compound 3
2.332(2)
O11−Cd1−O12
2.2970(19)
O13−Cd2−N34
2.353(2)
O24−Cd2−O15
2.339(2)
O24−Cd2−N37
2.376(2)
O13−Cd2−O15
Compound 4
2.411(3)
O2−Cd1−O1
2.264(4)
O3−Cd1−O1
2.364(3)
O2−Cd1−O4
2.480(3)
O1−Cd1−O4
2.288(3)
O2−Cd1−O3
2.625(3)
O2−Cd1−O13
2.268(3)
O12−Cd1−O1
2.382(3)
O2−Cd1−O12
2.399(3)
O12−Cd1−O3
2.323(3)
O12−Cd1−N26
2.417(3)
N26−Cd1−O1
2.459(4)
O2−Cd1−N26
Compound 5
2.2647(12)
O1−Cd1−O1
2.2465(11)
O2−Cd1−O1
2.3317(11)
O2−Cd1−O2
2.2801(11)
O1−Cd1−O3
2.3735(12)
O2−Cd1−O3
2.3857(11)
O3−Cd1−O3
2.1830(11)
O14−Cd2−O23
2.2645(12)
O14−Cd2−O4
2.5458(12)
O23−Cd2−O4
1.358(2)
O14−Cd2−O12
1.422(2)
O4−Cd2−O12
1.2467(18)
O14−Cd2−O13
54.28(6)
84.14(8)
85.03(7)
87.66(8)
105.36(8)
164.33(12)
103.23(11)
101.30(13)
84.91(11)
91.97(12)
88.51(13)
92.97(12)
92.93(14)
81.75(11)
138.18(12)
79.86(11)
86.07(12)
179.999(1)
90.77(4)
180.0
92.35(4)
82.41(4)
179.999(1)
150.36(4)
99.47(4)
89.13(4)
116.48(4)
91.03(4)
98.32(4)
by comparing the PXRD patterns of the bulk sample and simulated
one (Figure S3, Supporting Information). Anal. Calcd (%) for
C14H16NO15Cd2: C, 25.33; H, 2.41; N, 2.11. Found: C, 25.83; H, 2.68;
N, 2.05. Selected IR peaks (KBr disk, ν, cm−1): 1603, 1550
[υas(CO2−)], 1402 [υs(CO2−)], 1349, 1229 [υs(C−O)], and 3600−
3200 s.br [υ(O−H)] (Figure S2, Supporting Information).
{[Cd(fdc)(4,4′-bpy)(H2O)2]·EtOH}n (3). Similar synthetic procedure
as that for 1 was followed by using Cd(NO3)2·4H2O (154 mg, 0.5
mmol), 4,4′-bpy (78 mg, 0.5 mmol), fdc (78 mg, 0.5 mmol), water (6
mL), and ethanol (2 mL). Colorless X-ray-quality needle crystals of 3
(dimension, 0.20 × 0.04 × 0.01 mm3) were recovered in 68% yield
(based on Cd(II)). Phase purity was checked by comparing the PXRD
patterns of the bulk sample and simulated one (Figure S4, Supporting
Information). Anal. Calcd (%) for C34H26N4O13Cd2: C, 43.99; H,
2.69; N, 6.03. Found: C, 44.51; H, 2.89; N, 6.32. Selected IR peaks
(KBr disk, ν, cm−1): 1603, 1576 [υas(CO2−)], 1416 [υs(CO2−)], 1349,
1229 [υs(C−O)], and 3600−3200 s.br [υ(O−H)] (Figure S2,
Supporting Information).
[Cd(fdc)(1,2-bpe)(H2O)]n (4). The synthetic procedure is similar to
that of 3, only replacing 4,4′-bpy with 1,2-bpe, and the temperature is
140 °C. Colorless X-ray-quality needle crystals of 4 (dimension, 0.50 ×
0.02 × 0.01 mm3) were obtained. Yield: 40% (based on Cd(II)). Phase
purity was checked by comparing the PXRD patterns of the bulk
sample and simulated one (Figure S5, Supporting Information). Anal.
Calcd (%) for C30H25N3O13Cd2: C, 41.84; H, 2.90; N, 4.88. Found: C,
42.11; H, 3.02; N, 4.97. Selected IR peaks (KBr disk, ν, cm−1): 1602,
1578 [υas(CO2−)], 1430 [υs(CO2−)], 1376, 1229 [υs(C−O)], and
3600−3200 s.br [υ(O−H)] (Figure S2, Supporting Information).
and refined isotropically. For compound 4, the hydrogen atoms
bonded to the water molecule (O13) were not discernible from the
last final difference Fourrier maps and consequently were not included
in the structure refinement. In the final difference Fourier maps, there
were no remarkable peaks except the ghost peaks surrounding the
metal centers in all the compounds. A summary of crystal data and
relevant refinement parameters for compounds 1−5 are given in Table
1. Selected bond distances and angles for compounds 1−5 are listed in
Table 2.
Synthesis and Preliminary Characterization of the Compounds. [Cd(fdc)(2,2′-bpy)(H2O)]n (1). A mixture containing Cd(NO3)2·4H2O (154 mg, 0.5 mmol), 2,2′-bpy (156 mg, 1.0 mmol), fdc
(78 mg, 0.5 mmol), water (6 mL), and ethanol (2 mL) was sealed in a
Teflon-lined stainless steel vessel (23 mL), which was heated at 160
°C for 3 days and then cooled to room temperature. Pale colored
block crystals of 1 (dimension 0.20 × 0.12 × 0.06 mm3) were
obtained, collected, washed with distilled water, and dried in air. Yield:
47% (based on Cd(II)). Phase purity was checked by comparing the
PXRD patterns of the bulk sample and a simulated one from the single
crystal X-ray data (Figure S1, Supporting Information). Anal. Calcd
(%) C16H12N2O6Cd: C, 43.56; H, 2.72; N, 6.35. Found: C, 43.98; H,
2.39; N, 6.78. Selected IR peaks (KBr disk, ν, cm−1): 1643, 1590
[υas(CO2−)], 1470 [υs(CO2−)], 1442, 1376 [υs(C−O)], and 3600−
3200 s.br [υ(O−H)] (Figure S2, Supporting Information).
{[Cd(fdc)(pyz)(H2O)2][Cd(fdc)](H2O)2]·H2O}n (2). The same synthetic procedure as that for 1 was used except here 2,2′-bpy was
replaced by pyz and the solvent was only water (10 mL), giving
colorless needle X-ray-quality crystals of 2 (dimension, 0.40 × 0.06 ×
0.01 mm3) in 40% yield (based on Cd(II)). Phase purity was checked
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[{Cd2(fdc)2(H2O)4}·(1,2-bpe)]n (5). Phase pure compound 5 was
synthesized at 170 °C. At 150 °C, compounds 4 and 5 both
crystallized at the same time, while at 140 °C, we obtained the phase
pure compound 4. The rest of the process is similar to the synthesis of
4 by keeping Cd(NO3)2·4H2O (154 mg, 0.5 mmol), fdc (78 mg, 0.5
mmol), 1,2-bpe (91 mg, 0.5 mmol), water (6 mL), and EtOH (2 mL)
at 170 °C for 3 days in the autoclave and then cooling to room
temperature. Pale colored X-ray quality block shaped single crystals of
5 (dimension, 0.22 × 0.20 × 0.08 mm3) were precipitated. Yield: 52%
(based on Cd(II)). Phase purity of the compound was checked by
comparing the PXRD patterns of the bulk sample and simulated one
(Figure S6, Supporting Information). Anal. Calcd (%) for
C48H36N4O24Cd3: C, 41.43; H, 2.58; N, 4.02. Found: C, 41.82; H,
2.71; N, 4.29. Selected IR peaks (KBr disk, ν, cm−1): 1602, 1572
[υas(CO2−)], 1500 [υs(CO2−)], 1408, 1366 [υs(C−O)], and 3600−
3200 s.br [υ(O−H)] (Figure S2, Supporting Information).
MOFs, featuring important photoluminescence properties.
More fascinatingly, Cd ions can adopt a variety of coordination
numbers from four to seven in common,19 being able to adopt
different topological networks. Herein, we intend to modulate
the interplay of the different bridging ligands within the same
cadmium furandicarboxylate system. As a result, five new
coordination polymers have been constructed, and the
structural diversities are discussed. Closer observation on the
structures of 1−5 clearly reveals that different coordination
modes of the O-heterocyclic carboxylate and the different
bridging ligands lead them to adopt various different
topological structures.
Structure Description of [Cd(fdc)(2,2′-bpy)(H2O)]n (1).
Compound 1 crystallized in the space group Pc with Z = 4. In
the asymmetric unit of compound 1, the metal center is in
distorted pentagonal bipyramidal geometry. The basal plane of
the central metal ion is formed by the four oxygen atoms from
the two chelating fdc ligand and one nitrogen atoms from the
chelating bpy ligand (for CdA center O2A, O3A, O11A, O12A,
and N24A, respectively). The axial positions are occupied by
one water molecule (O1A) and another nitrogen atom of the
bpy ligand (N13A). ORTEP diagram with atom numbering
scheme has been shown in Figure 1. The Cd−O and Cd−N
■
RESULTS AND DISCUSSION
Synthesis of the Materials. The N/O-heterocyclic
carboxylic acids are very helpful to produce the metal−organic
frameworks with diverse dimensionality. In the recent past, a
variety of framework systems has been developed by using the
N/O-heterocyclic carboxylate ligands. It is also notable that the
heterocyclic carboxylic acids are very responsive toward the
external stimuli (like temperature, pH, solvent, etc.) to produce
different topological frameworks.16,17 In our recent work, we
have successfully developed 0D to 3D frameworks by changing
only the pH of the medium based on N-heterocyclic
carboxylate system.17a Maji et al. synthesized a new series of
frameworks in the N-heterocyclic carboxylate system by varying
the temperature.17b Recently, Ghosh et al. prepared a series of
Zn-based O-heterocyclic carboxylate frameworks with different
dimensionalities by tuning the reaction temperature.17c In this
study, we have developed a series of Cd-based furandicarboxylates by varying the bridging amine ligands. Here, the Oheterocylic carboxylate also shows a different bridging mode to
successfully construct the different molecular frameworks
(Scheme 1). It is worth mentioning that the deliberate use of
Figure 1. ORTEP diagram of compound 1 with 30% ellipsoid
probability.
bond distances are in the range of 2.287(3)−2.566(2) and
2.316(3)−2.385(2) Å, respectively, which are in well agreement
with the previously published works.19 These centers are
connected with each other in a double chelating fashion by the
fdc ligand forming a linear 1D infinite chain parallel to the
crystallographic b-axis (Figure 2). In the crystal packing, these
chains are strongly bonded with each other by the hydrogen
bonding mediated through the coordinated water molecules
and form supramolecular network in the crystallographic 3D
space as O(1A)−H(1A)···O(12B) [x − 1, y, z], O(1B)−
H(1B)···O(2A) [x, y − 1, z], O(1A)−H(2A)···O(3B) [x − 1, y
+ 1, z], O(1B)−H(2B)···O(11A) (Table S1, Supporting
Information).
Structure Description of {[Cd(fdc)(pyz)(H2O)2][Cd(fdc)](H2O)2]·H2O}n (2). Compound 2 crystallized in the
space group P21/n with Z = 4. The asymmetric unit is formed
by the two discrete one-dimensional part along with one
crystallographic water molecule. Both parts possess ladder type
chain structure (see ORTEP diagram, Figure 3). The first part
is formed by Cd1, fdc, and bridging pyz ligands (Figures 3 and
4), while the second part is exclusively formed by another Cd2
ion and fdc ligand (Figures 3 and 5). In both parts, Cd ions are
in distorted pentagonal bipyramid geometry. In part one, the
basal plane of the pentagonal bipyramid is formed by four
oxygen atoms from the two chelating fdc ligands (O3, O4, O12,
and O13) and one water molecule (O1) and the axial positions
Scheme 1. Bridging Modes of fdc Ligand Present in (i)
Compounds 1, 2, 3, and 4, (ii, iii) Compound 5, and (iv)
Compound 2
N-donor auxiliary ligands with the carboxylate ligands is also an
effective method for designing and constructing coordination
complexes. For example, 4,4′-bpy and its flexible derivative 1,2bpe show a great influence on the assembly process and have
been extensively used in the construction of a variety of MOFs
with different metal centers.12,18 The application of these
bridging N-donor ligands in MOF synthesis often results in
exceptional structures with unique motifs and useful functional
properties. Furthermore, it is notable that Cd has attracted
extensive interest as metal centers for the construction of
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Figure 2. One-dimensional chain of compound 1, propagating parallel to the crystallographic b-axis.
Figure 5. Ladder structure of part two in compound 2: (c) molecular
structure; (d) model structure of the ladder.
graphic a-axis (Figure 5). In the structure, these two parts are
bonded with each other through strong intra- and intermolecular hydrogen bonding interactions including multiple O−
H···O hydrogen bonds (Table S1, Supporting Information),
O(1)−H(1A)···O(17) [x, y − 1, z], O(1)−H(1A)···O(20) [x,
y − 1, z], O(1)−H(1B)···O(20) [−x, −y + 1, −z], O(2)−
H(2A)···O(4) [−x + 1/2, y − 1/2, −z + 1/2], O(2)−H(2B)···
O(19) [−x + 1/2, y − 1/2, −z + 1/2], O(17)−H(17A)···
O(13) [−x + 3/2, y + 1/2, −z + 1/2], O(17)−H(17B)···O(3)
[x, y + 1, z], O(18)−H(18A)···O(3) [−x + 1, −y + 1, −z],
O(18)−H(18A)···O(7) [−x + 1, −y + 1, −z], O(18)−
H(18B)···O(7) [−x + 1, −y + 1, −z], O(18)−H(18B)···O(12)
[−x + 1, −y + 1, −z], forming a supramoleculer 3D network.
Structure Description of {[Cd(fdc)(4,4′-bpy)(H2O)2]·
EtOH}n (3). Compound 3 crystallized in the space group P1̅
with Z = 4 and reveals a polycatenated MOF along with an
ethanol molecule in the crystal lattice. Here, both Cd centers
are in pentagonal bipyramidal geometry. The basal plane is
formed by the four chelating oxygen atoms (O14, O15, O23,
and O24) from the two different fdc ligands, and remaining one
is occupied by one nitrogen atom of the bridging 4,4′-bpy
ligand (N34); the axial positions are filled with one water
molecule (O13) and one nitrogen atom from another bridging
4,4′-bpy ligand (N37) (see ORTEP structure, Figure 6). The
Cd−O and Cd−N bond distances are in good agreement with
the previously reported works.19 These Cd centers are
connected alternatively by the bridging bpy ligand forming a
Figure 3. ORTEP diagram of compound 2 with 30% ellipsoid
probability, symmetry operation codes, i = −x, 1 − y, −z; ii = 1 − x, 1
− y, −z; iii = −x, 2 − y, −z; iv = 1 + x, y, z; v = −1 − x, 2 − y, −z.
are occupied by one water molecule (O2) and one nitrogen
atom from the bridging pyz ligand (N14). The Cd−O and Cd−
N bond distances are in well agreement with the previously
reported works.19 These centers are connected with each other
in a double chelating fashion (see Scheme 1, image i) by the fdc
ligand forming a linear 1D infinite chain parallel to the
crystallographic a-axis. These chains are further connected with
each other by the bridging pyz ligand forming the final ladder
type structure (Figure 4). On the other hand, in part two the
basal plane of the pentagonal bipyramid is formed by four
chelating oxygen atoms from the two fdc ligands (O19, O20,
O28, O29) and one μ2-O (O29*, * = 1 + x, y, z) from another
fdc ligand, and the axial positions are occupied by the two water
molecules (O17 and O18). These centers are connected with
each other (Scheme 1, image iv) by the fdc ligand forming a
linear 1D infinite ladder type chain parallel to the crystallo-
Figure 4. Ladder structure of part one in compound 2: (a) molecular structure; (b) model structure of the ladder.
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Figure 8. The simplified form of topological polycatenation among the
1D porous tubes present in compound 3.
Figure 6. ORTEP diagram of compound 3 with 30% ellipsoid
probability. Symmetry operation codes: i = −x, −y, −z; ii = −1 − x,
−y, −z; iii = 1 − x, −y, −z.
structure, there are two metal centers, Cd1 and Cd2, and both
are in the distorted pentagonal bipyramid geometry. The basal
plane of Cd1 is formed by four chelating oxygen atoms (O3,
O4, O12, and O13) from two fdc ligands and one nitrogen
atom from the bridging bipyridyl ligand (N26). The apical
positions are occupied by two water molecules (O1 and O2).
On the other hand, the basal plane of the Cd2 centers is formed
by four chelating oxygen atoms from the two fdc ligands (O15,
O16, O24, and O25) and one water molecule (O14). The axial
positions are occupied by the two nitrogen atoms (N37 and
N40) from the two different bpe ligands; the ORTEP diagram
with atom numbering scheme is shown in Figure 9. These Cd1
and Cd2 centers are bound with each other by the fdc and bpe
ligands and form Cd12Cd22 motifs, which propagate along the
crystallographic a-axis ultimately forming an S-type 1D strand.
These 1D strands are in turn interpenetrated with each other
forming a 1D + 1D → 3D framework (Figure 10). The
interpenetrated 1D strands are held to each other by strong
intramolecular O−H···O hydrogen bonds (Table S1, Supporting Information) (O(2)−H(2A)···O(3) [−x, −y + 1, −z − 1],
O(2)−H(2B)···O(16) [−x, −y + 1, −z], O(14)−H(14A)···
O(7) [x − 1/2, −y + 3/2, z + 1/2], O(14)−H(14A)···O(13)
[x − 1/2, −y + 3/2, z + 1/2], O(14)−H(14B)···O(4) [x − 1/
2, −y + 3/2, z + 1/2], O(14)−H(14B)···O(7) [x − 1/2, −y +
3/2, z + 1/2]) with O···O distances between 2.767(5) and
2.969(5) Å. Again to understand the structure of 4 clearly,
topological analysis by reducing multidimensional structure to a
square Cd4 motif, which is further linked via the fdc ligand in a
double chelating fashion and propagates parallel to the
crystallographic a-axis, ultimately forming a 1D tube-like
channel along that direction. These 1D tubes are again
interpenetrated with each other forming a 1D + 1D → 2D
polycatenated MOF (Figure 7). The polycatenated 1D tubes
are connected by intermolecular hydrogen bonding (O(1)−
H(1B)···O(11) [−x, −y − 2, −z]) among the terminal water
molecules and the carboxylate oxygen with H···O and O···O
distances of 1.89(2) and 2.712(3) Å, respectively. The ethanol
molecules are also entrapped within the channel by strong
intermolecular hydrogen bonding (O(1)−H(1A)···O(100) [x,
y − 1, z − 1] and O(100)−H(10)···O(2) [−x + 1, −y − 1, −z
+ 1]) with H···O and O···O distances of 1.94(4), 1.84(3), and
2.741(3) and 2.743 (3) Å (Table S1, Supporting Information),
respectively. To further understand the structure of 3,
topological analysis by reducing multidimensional structure to
a simple node and linker net was performed. The topological
analysis by TOPOS20 revealed that the structure is 4-c uninodal
net with point symbol 45.6 having vertex symbol [4.4.4.4.4.*].
The simplified form of topological polycatenation among the
1D porous tubes in the compound 3 is displayed in Figure 8.
Structure Description of [Cd(fdc)(1,2-bpe)(H2O)]n (4).
Compound 4 crystallized in the space group P21/n with Z = 4
and is also a 1D + 1D → 3D polycatenated framework. In the
Figure 7. (a) Supramolecular structure of compound 3 and (b) 1D + 1D → 2D polycatenation present in compound 3.
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Figure 9. ORTEP diagram of compound 4 with 30% ellipsoid probability. Symmetry operation codes: i = 1 − x, 2 − y, 1 − z; ii = −1 + x, y, z.
Figure 10. (a) 1D + 1D → 3D polycatenated 3D structure of compound 4 and (b) the 1D polymers that are penetrated with each other.
three chelating oxygen atoms of two fdc ligand (O12, O13, and
O24) and one carboxylate oxygen atom (O4). The apical
positions are occupied by one chelating oxygen atom (O23)
and one carboxylate oxygen atom (O14); the ORTEP diagram
with atom numbering scheme is shown in Figure 12. The Cd2
centers are bridged to the Cd1 centers in syn−anti fashion by
the fdc ligands, and the Cd2 centers are also connected with
each other in a double chelating fashion by the carboxylate
simple node and linker net was performed. The topological
analysis by TOPOS20 revealed that the structure possesses a
new binodal 3,4-c net with the point symbol {42.6}{44.62}
(Figure 11, see Supporting Information for detailed calculation).19d−f
Figure 11. Simplified topological view of compound 4 showing 1D +
1D → 3D polycatenation.
Structure Description of [{Cd2(fdc)2(H2O)4}·(1,2-bpe)]n
(5). Compound 5 crystallized in the space group P1̅ with Z = 1
and is a 2D layered framework with encapsulating the 1,2-bpe
ligands within the layers. In the asymmetric unit, there are two
types of metal centers, Cd1 and Cd2; both are in the distorted
octahedral geometry. Cd2 centers are more distorted than the
Cd1 centers. The basal planes of Cd1 centers are formed by
four water molecules (O1, O1*, O2, and O2*, * = 1 − x, 2 − y,
1 − z). The axial positions are filled with two carboxylate
oxygen atoms (O3 and O3*, * = 1 − x, 2 − y, 1 − z). On the
other hand, the basal planes of Cd2 centers are formed by the
Figure 12. ORTEP diagram of compound 5 with 30% ellipsoid
probability. Symmetry operation codes: i = 1 − x, 2 − y, 1 − z; ii = 2 −
x, 2 − y, 1 − z; iii = 1 − x, 1 − y, 1 − z.
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Figure 13. Three-dimensional supramolecular structure of compound 5 encapsulating the 1,2-bpe ligand (left) and 2D sheet structure present in the
compound 5 (right).
Compounds 4 and 5 are stable up to 200 °C; after losing the
water molecules, they continuously lose weight, and decomposition completes at around 400 °C (Figure 15).
ligand, forming a 2D dimensional network parallel to the
crystallographic ab-plane (Figure 13). In the structure, the 1,2bpe ligands are not connected to the metal centers and are
entrapped within the 2D layers by strong hydrogen bonds
(O(1)−H(1B)···N(36) [−x + 1, −y + 1, −z + 1]) with H···N
and O···N distances of 2.05(2) and 2.728(2) Å, respectively,
and π····π stacking with the average distance 3.9 Å.
Furthermore, the two water molecules O1 and O2 connected
to the Cd1 center established four O−H···O hydrogen bonds
with the fdc oxygens with O···O distances ranging from
2.728(2) to 2.914(2) Å (Table S1, Supporting Information).
Here also, topological analysis by reducing multidimensional
structure to a simple node and linker net was done, and the
study revealed that this structure also possesses a new topology
having binodal 4,6-c net with point symbol {32.42.52}{32.45.56.62}2 (Figure 14).19d−f
Figure 15. TG profiles of compounds 1−5.
Luminescent Properties. There exists a continuous
interest in discovering framework compounds with d10 metal
ions and organic chromophores, which have potential
application in the field of photoactive materials for sensing
(chemical sensors) and photochemistry.19,21 With the control
over synthesis, it is now possible to tune the photoluminescence properties of the desired frameworks.21,22 In
this regard, Cd(II) complexes having d10 electronic configuration demand much attention for their application potential
in luminescence properties. Hence, the preparation of Cd(II)
complexes can be an efficient method for developing new types
of luminescent materials. In the present report, the roomtemperature photoluminescence properties have been investigated for compounds 1−5 in solid state (Figure 16) and
compared with the respective free ligand. The emission
spectrum of compound 1 shows a band peaking at 410 nm,
which is the same as that of the fdc ligand (Figure S7,
Supporting Information). For compounds 2 and 3, the
emission spectrum deviates to the red relative to that of the
fdc ligands, peaking at 432 nm. The emission spectra of
compound 4 depend on the excitation wavelengths. For
excitation wavelengths between 300 and 400 nm, the emission
spectrum shows a peak around 420 nm resembling the free fdc
ligand emission (Figure S7, Supporting Information), whereas
at longer excitation wavelengths (400−450 nm), the emission
spectrum deviates to the red, peaking around 540 nm. This
Figure 14. Simplified topological view of compound 5.
Thermal Stability (TGA) Studies. Thermal stability of all
the compounds was checked in the temperature range RT to
800 °C. All compounds except compound 3 are stable up to
150−200 °C. Compound 1 is well stable up to 180 °C; then
after losing the coordinated water molecules (weight loss
4.11%, calcd 4.08%), it starts losing weight sharply and
decomposition completes at 380 °C. Compound 2 starts losing
water at 155 °C; after losing four water molecules in the first
step (weight loss 11.05%, calcd 10.85%), it loses another water
molecule at around 195 °C (weight loss 2.61%, calcd. 2.71%),
and then it continiously loses weight and completely
decomposes at 630 °C. The decay of compound 3 is slightly
complicated. It loses crystalline ethanol molecules first (weight
loss 5.01%, calcd 4.95%), then rapidly loses the water and
organic bridging ligand at 350 °C, and all the organic moieties
decompose at 650 °C, leaving the oxide as the product.
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{32.42.52}{32.45.56.62}2. The luminescence study reveals a
dependence of the emission spectra on the MOF structures
and proved the MOFs to be good luminescent materials with
tunable emission in the visible spectral range.
■
ASSOCIATED CONTENT
S Supporting Information
*
Hydrogen bonding table, TOPOS calculations, PXRD, and
more crystallographic information in cif format (CCDC
943517−943521). This material is available free of charge via
the Internet at http://pubs.acs.org.
■
Figure 16. Emission spectra of compounds 1 (350 nm), 2 (315 nm), 3
(320 nm), 4 (330 nm, solid line, and 400 nm, open circles), and 5
(405 nm). The excitation wavelength is indicated in parentheses.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: [email protected].
*E-mail: [email protected]. Tel: 351 234370368. Fax: 351 234370084.
Notes
latter component may result from the contribution of the 1,2bpe ligand, whose emission spectrum is formed of two
components around 440 nm19,21−23 and 520 nm,24 tentatively
assigned to intraligand n−π* and π−π* transitions. Despite the
presence of the same ligands, the emission spectra of
compound 5 are independent of the excitation wavelength,
revealing essentially the high-wavelength component from the
1,2-bpe ligand. The energy blue-shift observed between the
emission spectra of the free ligands and that of the compounds
was tentatively attributed to the presence of different kinds of
structural motifs.23 It has been suggested that the deviation of
the free ligand emission to the red can be assigned to an
enhancement of the p-conjugation due to the complexation of
the ligands to metal ions.25 Moreover, it is worth mentioning
that the different emission spectra of compounds 4 and 5
highlight the fact that the bonds established by the ligands and
the metal center also impact the emission properties.
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
R.S. thanks FCT for postdoctoral grants (SFRH/BPD/71798/
2010).This work was supported by FCT, POCI2010, PEst-C/
CTM/LA0011/2013, FSE, and FEDER.
■
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■
CONCLUSION
In summary, a series of Cd−fdc based MOFs with varied
bridging amine ligands has been synthesized and characterized
by different physicochemical methods and single crystal X-ray
diffraction. Compounds 1−5 show interesting topological
divergence. With the blocking amine, the 1D chain like
structure was obtained, while with flexible or rigid bridging
ligands, 1D ladder, 1D + 1D → 2D polycatenated MOF, 1D +
1D → 3D interpenetrated MOF, or simple layered 2D sheet
encapsulating the amine ligand were formed. It is quite
interesting to conclude that when the rigid 4,4′-bpy was used as
a bridging amine, we get a uniform 1D tube like morphology,
which are polycatenated with each other, but by using a flexible
amine, 1,2-bipyridylethene, two types of MOFs formed
depending on the temperature. In one case, the interpenetrated
3D framework formed with the interpenetrating units in wavy
S-like strands, while at higher temperature, the ligands are
encapsulated within the network through π···π interaction. For
small rigid spacer amines, like pyrazine, the network completely
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reveals a new topological binodal 4,6-c net having point symbol
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