Design and synthesis of two-dimensional pillared MOF layers by connecting infinite one-dimensional chains via 4,4′-bipyridine

Article abstract of DOI:10.1134/S1070328413030056

Two novel metal-organic frameworks, [Cd(Bna)(DMF)₂(H ₂O)₂] _n · nDMF (I) (Bna = 2,2′-dihydroxy-l,l′-dinaphthyl-3,3′-dicarboxylate) and [Cd(Bna)(Bipy)(DMF)₂] _n (II) (Bipy = 4,4′- bipyridine) have been synthesized under mild conditions and structurally characterized. Crystal structural analyses reveal that complex I adots a 1D spiral structure with DMF guest molecules in the spiral by hydrogen bondings. Complex II is constructed by -Cd-Bna-Cd- zigzag chains, which are further connected by Bipy into a 2D sheet. X-ray powder diffraction and thermogravimetric analyses for I and II show that they are highly themally stable in the solid state.

Full text of DOI:10.1134/S1070328413030056

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2013, Vol. 39, No. 3, pp. 239–244. © Pleiades Publishing, Ltd., 2013.
Design and Synthesis of TwoꢀDimensional Pillared MOF Layers
by Connecting Infinite OneꢀDimensional Chains via 4,4'ꢀBipyridine
1
L. J. Li*, L. Z. Wang, X. Y. Yang, G. Y. Wang, Ch. Tian, and J. L. Du
Key Laboratory of Chemical Biology of Hebei Province, Hebei University, Baoding, 071002 P.R. China
*
eꢀmail: llj@hbu.edu.cn
Received September 13, 2011
Abstract
—
Two novel metalꢀorganic frameworks, [Cd(Bna)(DMF) (H O) ] · n
DMF (
I
) (Bna = 2,2
ꢀbipyridine) have
been synthesized under mild conditions and structurally characterized. Crystal structural analyses reveal that
complex adots a 1D spiral structure with DMF guest molecules in the spiral by hydrogen bondings. Complex II
is constructed by Cd–Bna–Cd– zigzag chains, which are further connected by Bipy into a 2D sheet. Xꢀray
'ꢀdihyꢀ
2
2
2 n
droxyꢀl,l'ꢀdinaphthylꢀ3,3'ꢀdicarboxylate) and [Cd(Bna)(Bipy)(DMF) ] (II) (Bipy = 4,4
'
2
n
I
⎯
powder diffraction and thermogravimetric analyses for
solid state.
I
and II show that they are highly themally stable in the
DOI: 10.1134/S1070328413030056
1
INTRODUCTION
cation. Infrared spectra were obtained with a Nicoꢀ
let Impact 410 FTIR spectrometer in the range 400–
4000 cm using the KBr pellets. A PerkinElmer TGA
thermogravimetric analyzer was used to obtain therꢀ
Great progress has been made during the past two
–1
decades in the construction of metalꢀorganic frameꢀ
works (MOFs) comprising an infinite alternate arꢀ
rangement of metal ions and bridging ligands [1–3].
Because of the ability to systematically tune their poꢀ
rosity and the functionalities that are incorporated
within the framework scaffolds [4–9]. As a result, nuꢀ
merous MOFs have been engineered for a number of
potential applications, including gas storage [10–13],
nonlinear optics [8], and catalysis [14, 15]. Lin group
have particularly demonstrated the utility of binaphthꢀ
ylꢀderived homochiral MOFs in heterogeneous asymꢀ
metric catalysis [16, 17]. Although a number of strateꢀ
gies have been developed to achieve 2D or 3D strucꢀ
tures MOFs in recent years [9] it is still a challenge to
obtain MOFs with open channels and extremely large
porosity. Modification of the frameworks are still atꢀ
tractting much interest.
mogravimetric analysis (TGA) curve in air with a heatꢀ
1
ing rate of 20
at 25
°
C/min. H NMR spectra were run
°
C using a Bruker 400 (400 MHz) spectrometer.
Xꢀray powder diffraction (XRPD) spectra were obꢀ
tained with a Bruker D8 ADVANCE.
Synthesis of H Bna carried out acording to the folꢀ
2
lowing scheme:
COOH
COOH
FeCl
microwave
p = 20%
⋅
6H
O
OH
OH
3
2
OH
COOH
Presently, we have been interested in constructing
2
D structures MOFs containing Bna ligands, where
H Bna = 2,2 ꢀdihydroxyꢀl,l ꢀdinaphthylꢀ3,3 ꢀdicarꢀ
contributing to asymmetric synthesis. The
(H Bna)
2
'
'
'
2
A mixture of 3ꢀhydroxyꢀ2ꢀnaphthoic acid (9.4 g,
0 mmol) and FeCl3 6H O (20.3 g, 56 mmol) was
grinded sufficiency, the mixture was conducted in miꢀ
crowave tube at 70 C and 700 W for 35 min. The mixꢀ
ture was kept at room temperature with occasional
grinding for a certain period of the reaction time until
the reaction was completed. The residue was puried by
column chromatography on silica gel with petroleum
boxy acid
,
5
·
2
design strategy is to link 1D chains, made of the combiꢀ
nation of Bna and metal ion, to each other by using a linꢀ
ear ligand to form MOFs layers. The chains can be comꢀ
bined through linear bifunctional ligand such as 4,4'ꢀbiꢀ
pyridine (Bipy) to generate 2D MOFs architecture.
°
EXPERIMENTAL
ether–ethyl acetate (5 : 1) to afford the product H Bna
2
1
in 74% yield (7.0 g). Mp > 290
(CD ) CO; 400 MHz;
°
C; H NMR
Materials and methods. All chemicals were purꢀ
chased commercially and used without further puriꢀ
(
δ
, ppm): 7.14–7.17 (m., 2H,
Ar–H), 7.39–7.42 (m., 4H, Ar–H), 8.09 8.11 (m.,
2H, Ar–H), 8.84 (s., 2H, Ar–H); IR (KBr;
3 2
∼
1
–1
The article is published in the original.
ν
, cm ):
239

240
LI et al.
the up layer. The tube was then sealed. Diffusion beꢀ
tween the three phases over a period of 3 months proꢀ
duced transparent rhombic block crystals of II. IR
–1
(KBr;
ν
, cm ): 1640, 1581, 1399, 1455, 1110, 1110,
816, 758, 673, 598.
For C H N O Cd
34
3
8
4 8
C(5A)
anal. calcd., %: C, 57.93; H, 4.32; N, 7.11; Cd, 14.28.
Found, %: C, 57.45; H, 4.56; N, 7.08; Cd, 14.32.
O(9)
O(8)
O(1)
C(28)
O(6
A)
C(4)
C(6)
C(7)
C(8)
C(3)
N(2)
O(4) O(5)
C(21)
Xꢀray determination of structure. The single crystal
data of the complexes and II were collected on a
Bruker Smart Apex II CCD diffractometer using the
graphite monochromated Mo radiation (
were collected at 296(2) K.
A total of 17626 reections, including 6315 unique reꢀ
flections (Rint = 0.0163) were measured in the 1.97
< 28.34 . The data of II were collected at 296 K. A
total of 12540 reections, including 4205 unique reflecꢀ
tions (Rint = 0.0290) were measured in the 1.97
< 28.34 . Both structures were solved with a direct
C(26)
Cd(1)
O(7)
C(10)
C(5)
C(27)
C(2)
C(1)
I
O(2)
C(9)
C(22)
C(11)
C(12)
C(13)
C(14)
O(3)
O(10)
K
λ
=
C(25)
C(23)
N(1)
C(20)
α
O(6)
0.71073 Å). The data of I
C(29)
C(19)
C(30)
C(18)
C(17)
C(24)
°
<
N(3)
C(15)
O(11)
C(31)
θ
°
C(16)
°
<
Fig. 1. The coordination environment around Cd(II) in
with the thermal ellipsoid at the 30% probability level.
Symmetry code: ( ) – – 1/2, – 1/2, – + 1/2.
I
θ
°
method using SHELXSꢀ97 and were refined by fullꢀ
matrix leastꢀsquare methods using SHELXTLꢀ97. All
H atoms were placed geometrically. The crystalloꢀ
graphic data and structure experimental details of the
A
x
y
z
3
7
059, 1661, 1499, 1455, 1272, 1228, 1150, 1072, 886,
complexes
bond lengths and bond angles are presented in Table 2.
Supplementary material for structures and II has
been deposited with the Cambridge Crystallographic
I and II are given in Table 1, and selected
96, 736.
For C H O
14 6
I
22
anal. calcd., %:
Found, %:
C, 81.48;
C, 81.62;
H, 2.36.
H, 2.28.
Data Centre (nos. 836989 (
I
) and 836988 (II);
deposit@ccdc.cam.ac.uk
cam.ac.uk).
or
http://www.ccdc.
Synthesis of [Cd(Bna)(DMF) (H O) ] ⋅ nDMF (I).
A mixture of H Bna (7.5 mg, 0.02 mmol) and NaOH
1.6 mg, 0.04 mmol) was warmed to dissolved in 5 mL
2
2
2 n
2
RESULTS AND DISCUSSION
(
ethanol. After removing the solvents under a reduced
pressure, the residue was dissolved in 2 mL DMSO as
the under layer in a tube. A mixture of 1 mL DMSO
There are one [Cd(Bna)(DMF) (H O) ] and one
2
2
2
nonꢀcoordinated DMF guest molecules in the asymꢀ
metric unit of complex . As shown in Fig. 1, the
Cd(II) atom in is coordinated by two oxygen atoms
from two carboxylic groups of two independent Bna
ligands (Cd–O 2.246(2) and 2.260(2) ), two oxygen
layer. The tube was then sealed. Diffusion between the atoms from two DMF (Cd–O 2.273(3) and 2.263(2)
three phases over a period produced transparent block and two oxygen atoms from two H O (Cd–O 2.256(3)
I
and H O (1 : 1) was carefully layered as the middle layꢀ
2
I
er in the tube. 24.2 mg (0.08 mmol) Cd(NO3)2
·
6H O
2–
2
was dissolved in 2 mL DMF and H O (1 : 1) as the up
2
Å
Å)
2
–1
colourless crystals of
I. IR (KBr;
ν
, cm ): 1658, 1570, and 2.359(2)
cal positions to fulfill the octahedron coordination
motif. The dihedral angle between the pair of naphthyl
rings of the ligand is 88.1 and nearly perpendicular to
each other. The selected bond distances and angles of
complex are listed in Table 2. The extended structure
of features 1D spirals with Cd ions as the nodes
Fig. 2a). Here is an 1D chanel in the spiral, and the
nonꢀcoordinated guest DMF molecule is located in
the chanel by hydrongen bonded to the coordinated
water (O⋅⋅⋅O 2.640 ). Hydrogen bondings are also
found between water molecules from adjacent spiral
v/v = 1/1) was carefully layered as the middle layer in lines (O⋅⋅⋅O 2.799
) (Fig. 2b). It is interesting that the
the tube. A mixture of H Bna (7.5 mg, 0.02 mmol) and ligands from the two neighboring spiral are enantiꢀ
Å), where the latter two occupy the apiꢀ
1461, 1392, 1309, 1018, 940, 861, 751, 599.
For C H N O Cd
°
31
37
3 11
anal. calcd., %: C, 50.24; H, 5.00; N, 5.68; Cd, 15.19.
Found, %: C, 50.33; H, 4.86; N, 5.48; Cd, 15.15.
I
2+
I
(
Synthesis of [Cd(Bna) (Bipy)(DMF) ] (II). 34 mg
2
2 n
(0.12 mmol) Cd(NO)3
⋅
4H O was dissolved in a mixꢀ
2
ture of 2 mL DMSO and H O (v/v = 1/2) as the under
2
Å
layer in a tube. A mixture of 1 mL DMF and H O
2
(
Å
2
8
mg (0.04 mmol) Bipy was dissolved in 2 mL DMF as omer, leading to the opposite chirality of these two
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 3
2013

DESIGN AND SYNTHESIS OF TWOꢀDIMENSIONAL PILLARED MOF LAYERS
241
Table 1. Crystallographic data and details of the experiment for complexes
I
and II
Value
Parameter
I
II
Formula weight
Crystal system
Space group
740.05
787.09
Monoclinic
Orthorhombic
P
2 /
n
C2221
1
a
, Å
, Å
12.9178(4)
11.4056(4)
23.0528(7)
90.9520(10)
3396.02(19)
4
11.7689(11)
13.8060(13)
20.708(2)
90
b
c
, Å
β
, deg
Volume, Å3
3364.6(6)
4
Z
ρ
calcd
, g/cm3
1.447
1.554
μ
, mm–1
(000)
Crystal size, mm
Range for data collection, deg
0.704
0.711
F
1520
1608
0.46
1.77 to 28.31
–17 < < 17,
15 < k < 14,
20 < < 30
21088
×
0.26
×
0.21
0.27
1.97 to 28.34
–15 < < 15,
–8 < k < 18,
–27 < < 27
×
0.09
×
0.08
θ
Limiting indices
h
h
–
–
l
l
Reflections collected
12540
Independent reflections
8212 (Rint = 0.0170)
4205 (Rint = 0.0290)
Completeness to
Goodnessꢀofꢀfit on F2
θ
, %
97.3
1.053
440
100.0
1.596
237
Parameters
Final
indices (all data)
Largest diff. peak and hole,
R
indices (
I
> 2
σ
(
I
))
R1 = 0.0398
wR2 = 0.1085
R1 = 0.0297
wR2 = 0.0568
R
R1 = 0.0498
wR2 = 0.1171
R1 = 0.0349
wR2 = 0.0577
e
Å–3
1.013 and –0.410
0.939 and –0.333
2+
neighboring spiral lines. These spirals with opposite plane (Fig. 4b) with Cd ions as the nodes. There isn’t
chirality pack alternatively along axis (Fig. 2b), strong interactions (Hꢀbonding or p–p stacking) are
makes the structure of complex achiral.
found between adjacent sheets (Fig. 4c).
y
I
There are 1/2[Cd(Bna)(Bipy)(DMF) ] in the
Both in and II, the phenolic hydroxyl of Bna is
I
2
asymmetric unit of complex II. As shown in Fig. 3, the uncoordinated with any metal ion, just forms intramoꢀ
Cd(II) atom in II is coordinated by two oxygen atoms lecular hydrogen bondings with O from the adjacent
from two carboxylic groups of two independent Bna2
–
carboxylate groups (O⋅⋅⋅O 2.52 and 2.56 Å, repectiveꢀ
ligands (Cd–O 2.3054(19)
two DMF (Cd–O 2.330(2)
from two Bipy (Cd–N 2.321(2) and 2.378(2)
Å
Å
), two oxygen atoms from ly).
) and two nitrogen atoms
),
IR study shows that the characteristic absorption
Å
–1
band of Bipy gives bands at 1591, 1410, 808, 607 cm ,
where the latter two N occupy the apical positions to
fulfill the octahedron coordination motif. The diheꢀ
dral angle between the pair of naphthyl rings of the
–1
while they move to 1581, 1399, 816, 598 cm in comꢀ
plex II. This assumed that the N atoms of the Bipy
have coordinated with the metal ions.
ligand is 78.6
°
. The selected bond distances and angles
2+
What’s more, IR shows that the characteristic abꢀ
sorption band of C=O gives at 1660 cm , C–O gives
are listed in Table 2. The Cd ions connect the adjaꢀ
–1
2–
cent Bna ligands to form an infinite 1D zigzag line
Fig. 4a), and then coordinate with Bipy molecules at at 1227 cm , while they, respectively, move to 1640
–1
(
–1
apical positions to extend to a 2D sheet along y–z and 1110 cm and from the IR, we observed that the
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
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2013

242
LI et al.
Table 2. Selected bond lengths (Å) and bond angles (deg) for complexes
I
and II*
Bond
d
, Å
Bond
d, Å
I
O(11)–Cd(1)
Cd(1)–O(10)
Cd(1)–O(3)
2.272(3)
2.259(2)
2.254(3)
Cd(1)–O(5)
2.243(2)
2.360(3)
2.261(2)
Cd(1)–O(14)
Cd(1)–O(1)
II
Cd(1)–O(2)#1
Cd(1)–O(4)#1
Cd(1)–N(1)
2.3064(19)
2.329(2)
2.325(2)
Cd(1)–O(2)
Cd(1)–O(4)
Cd(1)–N(2)#2
2.3064(19)
2.329(2)
2.378(2)
Angle
ω
, deg
Angle
ω
, deg
I
O(5)Cd(1)O(3)
O(5)Cd(1)O(1)
O(5)Cd(1)O(11)
O(1)Cd(1)O(11)
O(10)Cd(1)O(14)
O(3)Cd(1)O(10)
O(10)Cd(1)O(1)
O(11)Cd(1)O(14)
88.66(12)
93.30(11)
178.59(12)
86.99(12)
88.01(10)
90.69(12)
175.14(11)
87.72(13)
O(5)Cd(1)O(10)
O(3)Cd(1)O(1)
O(3)Cd(1)O(11)
O(5)Cd(1)O(14)
O(1)Cd(1)O(14)
O(10)Cd(1)O(11)
O(3)Cd(1)O(14)
89.53(11)
93.32(14)
89.94(15)
93.67(10)
87.88(11)
90.27(12)
177.32(12)
II
#
1
#1
O(2) Cd(1)O(2)
166.86(13)
91.68(8)
87.85(8)
175.97(19)
180.0
O(2) Cd(1)N(1)
96.57(7)
87.86(8)
2.330(2)
83.43(7)
87.98(10)
92.02(10)
83.43(7)
#1
#1
O(2)Cd(1)O(4)#1
O(2)Cd(1)O(4)
O(2) Cd(1)O(4)
#1
O(2) Cd(1)O(4)
#1
#1
#2
O(4) Cd(1)O(4)
O(2) Cd(1)N(2)
N(1)Cd(1)N(2)#2
O(2)Cd(1)N(1)
O(4) Cd(1)N(2)
#1
#2
96.57(7)
92.02(10)
87.98(10)
N(1)Cd(1)O(4)
#
1
O(2)Cd(1)N(2)#2
C(13) C(14)C(15)
O(4)Cd(1)N(2)#2
*
Codes symmetry: #1
–x
– 1/2,
y
– 1/2, –
z
+ 1/2, #2
–x
– 1/2,
y
+ 1/2, –
z
+ 1/2 for
I
; #1
x, –y
+ 1, –
z
+ 1, #2
x
+ 1,
y,
z
for II
.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
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2013

DESIGN AND SYNTHESIS OF TWOꢀDIMENSIONAL PILLARED MOF LAYERS
243
(a)
(b)
Fig. 2. The 1D spiral structure of
I
(a); the packing arrangement of
I
, viewed along y axis (b).
N(2)
C(17A)
C(17)
C(16)
C(16
A)
C(15)
C(14)
C(13A)
C(19)
C(13)
C(12
N(1)
A
)
N(3)
C(9)
C(8)
C(11)
C(20) C(10)
C(12)
C(18)
O(1)
O(4)
Cd(1)
N(2
C(7)
C(1)
O(2)
C(2)
O(2A)
C(4) C(5)
C(6)
C)
C(3)
O(4A)
C(6B)
O(3)
O(3
C(7
C(8
C(9
B
)
C(4B)
B
)
B
)
C(3B
)
B
)
C(2
B)
C(11B)
O(2B)
C(1B)
O(1B)
Fig. 3. The coordination environment around Cd(II) in II with the thermal ellipsoid at the 30% probability level. Symmetry code:
, – + 1, – + 1; ( ) – + 2, , – + 3/2; ( + 1,
(A)
x
y
z
B
x
y
z
C)
x
y, z.
the characteristic absorption band of phenolic hydroxꢀ
TGA shows that complex II (Fig. 5b) is stable up to
–1
yl at 1455 cm has no change. This assumed that the 200
phenolic hydroxyl was uncoordinated with the metal weight loss steps. The first weight loss of 23.02% from
ions, which assured the freedom of the active centres.
C is corresponded to the loss of
°
C. The TG curve of complex II showed three
2
05 to 265
two DMF molecules. The second weight loss of 5.51%
between 265 and 324 C is attributed to the loss of one
°
TGA shows that complex is stable up to 110 C.
I
°
°
The TG curve of complex showed four weight loss
steps (Fig. 5а). The first weight loss of 14.9% from 110 Bipy molecule. The third weight loss of 57.56% is attribꢀ
to 150
C is corresponded to the loss of one guest DMF uted to the loss of all organic ligands and the residue is
and two water molecules. The second weight loss of CdO.
3.4% between 153 and 275 C is attributed to the loss
of two DMF molecules. The last weight loss of 46.7%
is attributed to the loss of all organic ligands and the ment XRPD pattern of complex II. The results asꢀ
residue is CdO. sume that the individual single crystalline structural
I
°
2
°
We comprised the imitation and actual measureꢀ
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
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2013

244
LI et al.
(а)
(c)
x
0
z
(b)
y
Fig. 4. The 1D –Cd–Bna–Cd– zigzag line of II (a); schematic representation of the 2D chiral sheet (b); the packing arrangement
of II, viewed along the axis (c).
x
is as the same as the huge mass small crystalline
structural.
ACKNOWLEDGMENTS
This work was supported by the Natural Science
Foundation of Hebei Province (nos. B2010000223,
B2012201109).
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I (a)
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2013