4-Carboxylphthalhydrazidate-bridged layered Pb(ii) coordination polymers

Article abstract of DOI:10.1039/b922767a

The hydrothermal in situ self-assembly of Pb²⁺, benzene-1,2,4-tricarboxylic acid (BTCA) and N₂H₄· H₂O created two Pb(ii) coordination polymers containing 4-carboxylphthalhydrazidate (CPTH), [Pb(CPTH)(phen)] (phen = 1,10-phenanthroline) 1 and [Pb₄(OH)₂(H₂O) ₃(CPTH)₃]·2H₂O 2. CPTH is derived from the in situ acylation reaction of BTCA with N₂H₄· H₂O. The Royal Society of Chemistry 2010.

Full text of DOI:10.1039/b922767a

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PAPER
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4-Carboxylphthalhydrazidate-bridged layered Pb(II) coordination polymers†
Juan Jin, Ming-Jun Jia, Yu Peng, Qin Hou, Jie-Hui Yu* and Ji-Qing Xu*a
a
c
a
a
ab
Received 2nd November 2009, Accepted 6th January 2010
First published as an Advance Article on the web 28th January 2010
DOI: 10.1039/b922767a
2+
The hydrothermal in situ self-assembly of Pb , benzene-1,2,4-tricarboxylic acid (BTCA) and
$H O created two Pb(II) coordination polymers containing 4-carboxylphthalhydrazidate
(OH) (H O) (CPTH) ]$2H
$H O.
N
2
H
4
2
(
CPTH), [Pb(CPTH)(phen)] (phen ¼ 1,10-phenanthroline) 1 and [Pb
4
2
2
3
3
2
O 2.
CPTH is derived from the in situ acylation reaction of BTCA with N
2
H
4
2
Introduction
In the past two decades, much effort has been taken to the study
on the design and synthesis of novel metal–organic frameworks
(
MOFs) owing to the fascinating topologies and the potential
2
1
applications in the fields of gas adsorption, ion-exchange,
3
4
5
6
optics, electrochemistry, magnetism and catalysis. So far,
a number of novel MOFs with various topological structures
have been obtained by the direct construction of metal ions and
organic bridging N/O/S-donor ligands. But in reported MOFs,
most applied organic ligands are commercially available or pre-
synthesized. The typical examples are the bridging multi-dentate
N-heterocyclic ligands, polycarboxylic acids, pyridine poly-
carboxylic acids and similar species. Recently, the in situ ligand
synthesis provides a new approach towards the crystal engi-
Scheme 1
CPTH is derived from the hydrothermal acylation reactions
2 4 2
between 1,2,4-BTCA and N H $H O (see Scheme 1).
Experimental
7
neering of MOFs. Based on this strategy, the reactions between
Materials and physical measurement
metal salts and ligand precursors have created some novel MOFs
under the hydrothermal condition. The organic ligands appear-
ing in the resulting frameworks are derived from the in situ
reactions of the ligand precursors. It is said that the synchronous
in situ production for the ligands favour the growth of the
crystals. To data, more than ten kinds of in situ ligand reactions
All chemicals were of regent grade quality and obtained from
commercial sources without further purification. Elemental
analysis (C, H and N) was performed on a Perkin-Elmer 2400LS
II elemental analyzer. Infrared (IR) spectra were recorded on
ꢀ
1
a Perkin Elmer Spectrum 1 spectrophotometer in 4000–400 cm
7
have occurred under hydrothermal conditions including the
8
hydroxylation of aromatic rings, the cycloaddition of organo-
region using a powdered sample on a KBr plate. Thermogravi-
metric (TG) behaviour was investigated on a Perkin-Elmer
9
nitriles with azides, the decarboxylation of aromatic carboxyl-
ꢁ
ꢀ1
TGA-7 instrument with a heating rate of 20 C min in air.
Fluorescence spectrum in solid state was obtained on a LS 55
florescence/phosphorescence spectrophotometer at room
temperature.
10
ates, etc. From in situ ligand acylation reactions of aromatic
carboxylates with organic amines, several novel MOFs with the
11
extended structures have been reported. Most of the reported
MOFsare basedontransitionmetalorrare-earthmetal ions, while
Pb(II)-containing MOFs are less developed until now. Herein, we
will report the preparation and structural characterization of two
Synthesis of the title compounds
CPTH-bridged
layered
Pb(II)
(OH)
coordination
(H O) (CPTH)
polymers
]$2H O 2.
The reactions were carried out in 30 mL Teflon-lined stainless
steel vessels under autogenous pressure. The single crystals were
collected by filtration, washed with distilled water and dried in air
at ambient temperature.
[
Pb(CPTH)(phen)] 1 and [Pb
4
2
2
3
3
2
a
College of Chemistry and State Key Laboratory of Inorganic Synthesis
and Preparative Chemistry, Jilin University, Changchun, 130023, P. R.
China. E-mail: jiehuiyu@yahoo.com.cn; jhyu@jlu.edu.cn; xjq@mail.jlu.
edu.cn
[Pb(CPTH)(phen)] 1. The yellow block crystals of 1 were
obtained
by
the
hydrothermal
self-assembly
of
b
State Key Laboratory of Coordination Chemistry, Nanjing University,
Nanjing, Jiangsu, 210093, P. R. China
Pb(CH COO) $3H O (100 mg, 0.52 mmol), BTCA (200 mg,
3
2
2
c
0.53 mmol), N H $H O (0.10 ml) and phen$H O (100 mg,
2 4 2 2
Key Laboratory of Surface and Interface Chemistry of Jilin Province,
College of Chemistry, Jilin University, Qianjin Road 2699, Changchun,
0.50 mmol) in a 15 mL aqueous solution (pH ¼ 7 neutralized by
130012, China
ꢁ
N H $H O) at 170 C for 4 d. Yield: 35% based on Pb. Anal.
4
2
2
† Electronic supplementary information (ESI) available: Supplementary
details. CCDC reference numbers 752419 (1) and 752420 (2). For ESI and
crystallographic data in CIF or other electronic format see DOI:
10.1039/b922767a
calcd PbC21
12 4 4
H N O 1: C 42.64, H 2.04, N 9.47%; Found: C
ꢀ1
4
2.51, H 2.24, N 8.48%. IR (cm ): 1636 m, 1572 s, 1530 m,
1484 m, 1428 s, 1358 s, 1211 m, 1120 m, 858 m, 768 s, 713 s.
1
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[
Pb (OH) (H O) (CPTH) ]$2H O 2. The yellow block crys-
4 2 2 3 3 2
Results and discussion
tals of 2 were obtained by another hydrothermal self-assembly of
Pb(CH COO) $3H O (100 mg, 0.52 mmol), BTCA (200 mg,
Structure description
3
2
2
0
0
.53 mmol), N
2
H
4
$H O (0.10 ml) and piperazine$6H
2
2
O (97 mg,
[
Pb(CPTH)(phen)] 1. Single-crystal X-ray analysis revealed
.50 mmol)/triethylenediamine$6H O (114 mg, 0.50 mmol) in
2
that compound 1 is a CPTH-bridged layered Pb(II) coordination
polymer with ancillary phen molecules. The CPTH ligands using
the hydroxylimino O atom (O1), hydroxylimino N atom (N1)
and one carboxyl O atom (O3) first bridge the Pb(II) centers into
a 1D endless chain with two types of macroporous rings
a 15 mL aqueous solution (pH ¼ 8 neutralized by N
2 4 2
H $H O) at
ꢁ
1
70 C for 4 d. Yield: 15% based on Pb. Anal. calcd
4 27 24 6
Pb C H N O19 2: C 20.72, H 1.55, N 5.37%; Found: C 21.08, H
ꢀ1
1.54, N 5.62%. IR (cm ): 1666 s, 1616 m, 1556 s, 1488 s, 1465 s,
1376 s, 1355 s, 1312 s, 1220 m, 1128 m, 1071 m, 823 m, 779 m,
702 m. Even though the piperazine/triethylenediamine did not
8
-membered A and 16-membered B arranging along the b-axis in
the order of ABAB (see ESI, Fig. S1).† The Pb–O bond lengths
ꢀ
appear in the final framework, without them the aim product was
not obtained. Maybe their presences offer a mild basic environ-
ment for the reaction.
(
Pb–Ohydroxylimino ¼ 2.310(5), Pb–Ocarboxyl ¼ 2.423(4) A) and
ꢀ
Pb–Nhydroxylimino bond length (2.673(5) A) are comparable with
11a
those found in reported similar compounds. The shortest Pb/
ꢀ
Pb separation observed in ring A is 4.745 A. The acylamino O
atoms of CPTH liands bind further to the Pb(II) centers of the
ꢀ
adjacent 1D chain with a Pb–O distance of 3.084 A, extending
X-Ray crystallography
the 1D chain into a 2D layer as shown in Fig. 1(a). Even though
this Pb–O bond is rather longer, it is by far shorter than that of
ꢀ
Data were collected with Mo Ka radiation (l ¼ 0.71073 A) on
ꢀ
12
3.24(5) A observed in Pb BiPO . The topological structure of
a Siemens SMART CCD diffractometer for 1 and on a Rigaku
R-AXIS RAPID IP diffractometer for 2. With the SHELXTL
program, compound 1 was solved using direct methods and
compound 2 using heavy atom methods. All were refined by
full-matrix least-squares techniques. The non-H atoms were
assigned anisotropic displacement parameters in the refinement
and the H atoms were treated using a riding model. Only the H
atoms bonded to C and N atoms were allowed for in the model
and no H atoms bound to O atoms were in the model. The
2 6
the 2D layer (Fig. 1b) indicates that both the Pb center and the
CPTH ligand act as 4-connected nodes. Fig. 2 is the projection
plot of compound 1 in the ac plane. Two structural factors
stabilize the layer framework of compound 1: both ring A and
ring B adopt the chair-type configurations; the neighbouring
CPTH ligands between the chains stack together via the offset
face-to-face p/p interactions with an interplanar distance of
ꢀ
ꢀ
ca. 3.45 A and a centroid–centroid separation of ca. 3.50 A.
2
structures were then refined on F using SHELXL-97. CCDC
numbers of compounds 1 and 2 are 752419 and 752420,
respectively. Basic information pertaining to the crystal
parameters and structure refinement of the compounds is
summarized in Table 1. Selected bond lengths and angles are
listed in the ESI, Table S1.†
Table 1 Crystal data and structure refinement for the title compounds
1
2
Empirical formula
M
T/K
PbC21
591.54
293(2)
Monoclinic
C2/c
21.5673(11)
10.1496(5)
16.1354(5)
H
12
N
O
4 4
4 27 24 6 19
Pb C H N O
1565.28
293(2)
Triclinic
Crystal system
Space group
ꢁ
P1
ꢀ
a/A
10.594(2)
10.716(2)
14.990(3)
85.91(3)
80.52(3)
89.68(3)
1674.1(6)
2
ꢀ
b/A
ꢀ
c/A
a/
ꢁ
ꢁ
b/
94.849(3)
ꢁ
g/
V/A
ꢀ
3
3519.4(3)
8
2.233
9.628
2240
Z
D
3
c
/g cm
3.105
20.149
1416
ꢀ
1
m(Mo Ka)/mm
F(000)
Total data
Unique data
12 459
4348
16 597
7579
R
Data I > 2s(I)
GOF
int
0.0933
3340
1.007
0.0404
0.1031
0.0461
6602
1.113
0.0384
0.1105
Fig. 1 The 2D layer structure (a) and its topological plot (b) in
[Pb(CPTH)(phen)] 1 (phen rings are omitted for clarity; d: ꢀx + 1, y,
R
wR [all data]
1
[I > 2s(I)]
2
ꢀz + 0.5).
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by two cis carboxyl O atoms (O3d, O11a) (Pb4–O3d ¼ 2.635(6),
ꢀ
Pb4–O11a ¼ 2.680(5) A), one hydroxylimino N atom (N5) (Pb4–
ꢀ
N5 ¼ 2.484 A), one hydroxylimino O atom (O9) (Pb4–O9 ¼
ꢀ
.693(7) A) together with three Ow molecules (Ow1, Ow2, Ow5)
2
ꢀ
(
Pb4–Ow1 ¼ 2.728(9), Pb4–Ow2 ¼ 2.584(7), Pb4–Ow5 ¼ 2.801 A).
Only around Pb4, one chelating hydroxylimino group is
observed. As shown in the ESI, Fig. S4,† three CPTHs ligands
exhibit the new different bridging modes. CPTH I adopts
4
a m -bridging mode with the carboxyl group bridging three Pb
centers and the hydroxylimino O atom bridging one Pb center.
The coordination mode of the carboxyl group in CPTH II is the
same as that in CPTH I, but the hydroxylimino O atom bridges
two Pb centers. CPTH III adopts a special m -bridging mode: the
5
carboxyl group chelates to one Pb center, and one carboxyl O
atom further binds to another Pb center; the hydroxylimino
group chelates to one Pb center, and the hydroxylimino O atom
further binds to two Pb centers.
Fig. 2 The projection plot of [Pb(CPTH)(phen)] 1 in the ac plane.
The phen rings protrude out from the layer, and arrange regu-
larly on both sides of the layer. Owing to the interdigitation of
the adjacent phen molecules between the layers via the offset
face-to-face p/p interactions characterized by an interplanar
The Pb centers, hydroxyl O atoms, CPTH O atoms as well as
the coordinated Ow molecules congregate together into a 1D
infinite Pb–O ribbon as shown in Fig. 3. The basic repeat unit of
this ribbon is a tetranuclear Pb–O cluster (Pb1–Pb4), consisting
of four Pb atoms linked together by two carboxyl O atoms
(O7a, O9), two hydroxylimino O atoms (O11a, O5) and two
hydroxyl O atoms (OH2, OH1) as the bridges. The tetranuclear
cluster, via an inversion center, is propagated into an octanuclear
ꢀ
distance of 3.54 A and a centroid–centroid separation of ca.
ꢀ
.75 A, the 2D layers are propagated into a 3D supramolecular
3
network. The crystallographically unique Pb1 center in
compound 1 is six-coordinated, surrounded by one hydrox-
ylimino O atom (O1a), one hydroxylimino N atom (N1), one
carboxyl O atom (O3b), one acylamino O atom (O2d) as well
as two phen N atoms (N3, N4), and the CPTH ligand exhibits
cluster through m
Furthermore, all the octanuclear clusters are linked together into
the 1D endless ribbon through the bridging role of m -mode O3a,
O3e and m -mode OH2, OH2b. The shortest Pb/Pb contact in
3
-mode O9, OH1, OH1b and O9b bridges.
a m
4
-bridging mode (ESI, Fig. S2).†
2
3
ꢀ
[
Pb
4
(OH) (H O) (CPTH) ]$2H O 2. The simple self-assembly
2
2
3
3
2
the ribbon is Pb2/Pb2b ¼ 3.942 A. In the ab plane, all the
CPTH ligands arrange parallel to each other, bridging the Pb–O
ribbons into a 2D layer as shown in the ESI, Fig. S5.† Fig. 4(a) is
the projection plot of compound 2 in the ac plane. Obviously,
compound 2 contains a double-layered structure. The CPTH
ligands array in two lines between the ribbons, supporting the 1D
ribbons to form the 1D channels within the layers. In the
formation of the channels, the existence of hydroxyl groups in
the ribbon and their distribution in the middle of the ribbon play
a key role. Between the layers, the neighbouring acylamino
groups head-to-head form the hydrogen bonded dimers via the
N–H/O interactions, through which, all the 2D layers are
2+
of the Pb salt and ligand precursors without phen created
another CPTH-bridged layered Pb(II) coordination polymer of
compound 2. The layered structure of compound 2 is more
complex than that of compound 1. The asymmetric unit consists
of four Pb(II) atoms, three CPTH ligands, two OH groups, three
w w
coordinated O molecules as well as two lattice O molecules. As
show in the ESI, Fig. S3,† Pb1 is in a tetragonal pyramidal site
with two cis carboxyl O atoms (O3a, O7a) (Pb1–O3a ¼ 2.673(6),
ꢀ
Pb1–O7a ¼ 2.637(6) A) and two cis hydroxylimino O atoms
ꢀ
(
O1, O5) (Pb1–O1 ¼ 2.426(6), Pb1–O5 ¼ 2.400(6) A) on the
equatorial plane, and one hydroxyl O atom (OH2) (Pb1–OH2 ¼
ꢀ
.226(5) A) on the axis. Pb2 is also coordinated by four CPTH
2
self-assembled into a 3D supramolecular network. The
ligands in addition to two hydyoxyl O atoms (OH1, OH1b)
ꢀ
(
Pb2–OH1 ¼ 2.470(5), Pb2–OH1b ¼ 2.498(5) A). Four CPTH
ligands contain the similar arrangement to that around Pb1
except one carboxyl group chelating to the Pb2 center. The
chelating Pb–O bond lengths (Pb2–O12a ¼ 2.612(6), Pb2–O11a
ꢀ
2.626(6) A) are slightly shorter than that of the monodentately
¼
ꢀ
bridging one (Pb2–O7a ¼ 2.707(6) A). Due to the higher coor-
dination of seven for Pb2, the Pb–Ohydroxylimino distances of
ꢀ
Pb2–O5 ¼ 2.738(6) and Pb2–O9 ¼ 2.660(5) A are obviously
longer than those around Pb1. Pb3 is six-fold coordinated by two
trans carboxyl O atoms (O8c, O4d), one hydroxylimino O atom
(
O9b) as well as two hydroxyl O atoms (OH1, OH2b) (Pb3–OH1
ꢀ
¼
2.374(5), Pb3–OH2b ¼ 2.346(5) A). The shortest Pb–O
carboxyl
ꢀ
distances (Pb3–O8c ¼ 2.507(7), Pb3–O4d ¼ 2.569(6) A) and the
ꢀ
longest Pb–Ohydroxylimino distance (Pb3–O9b ¼ 2.855 A) in
Fig.
4 2 2 3 3 2
3 The Pb–O ribbon in [Pb (OH) (H O) (CPTH) ]$2H O 2
compound 2 are found around Pb3 due to the trans arrangement
(a: x ꢀ 1, y, z; b: ꢀx ꢀ 2, ꢀy + 2, ꢀz + 1; c: ꢀx ꢀ 1, ꢀy + 2, ꢀz + 1;
d: x ꢀ 1, y + 1, z; e: x + 2, y ꢀ 2, z ꢀ 1).
of two CPTH ligands. The seven-coordinated Pb4 is surrounded
1
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Scheme 2
Table 2 C–O distances of CPTH ligands in the title compounds
2
1
I
II
III
C]O
ꢀ
1.242(7)
1.312(7)
1.239(9)
1.294(9)
1.251(9)
1.318(9)
1.259(9)
1.293(9)
C–O
group and the hydroxylimino group as the donors coordinates to
the metal centers. Sometimes the acylamino O atom also
participates in the coordination to the metals as observed in
compound 1. No examples show that the acylamino N atom has
the reactivity, and could also coordinate to the metals. The
adjacent acylamino groups are easier to form the hydrogen-
bonded dimer via the N–H/O interactions as observed in
compound 2. In compounds 1 and 2, 4-CPTH exhibits four-types
of bridging modes. Another bridging mode for 4-CPTH is found
Fig. 4 The projection plot of [Pb
ac plane (a) and the water cluster structure between the layers (b) (f: ꢀx,
y + 1, ꢀz; g: x ꢀ 2, y + 1, z).
4 2 2 3 3 2
(OH) (H O) (CPTH) ]$2H O 2 in the
ꢀ
hydrogen-bonded parameters are listed in Table S2.† The lattice
molecules Ow3 and Ow4 are filled in the space between the
layers. It is noteworthy that two Ow3, two Ow4, two coordinated
w1 as well as two coordinated Ow2 aggregate together to form
an octanuclear water cluster (H O) as shown in Fig. 4b. This
0
in compound [Co(CPTH)(bpy)] (bpy ¼ 2,2 -bypyridine), which is
O
w
the unique example of reported 4-CPTH-bridged coordination
3
polymer. In this compound, 4-CPTH adopts a m -bridging mode
O
with the hydroxylimino N atom and the acylamino O atom
coordinating monodentately to the Co centers, respectively, and
with the carboxyl O atoms chelating bidentately to one Co center
2
8
water octamer has a chair-like hexamer at the core with two
additional water molecules in the 2,5-positions of the hexamer
11b
(
see the ESI, Fig. S7).†
(
see the ESI, Fig. S6).† So far, the report on crystallographically
13
characterized (H O)8 water is limited. The average O /O
ꢀ
interaction of 2.84 A in the hexamer is equal to that of 2.85 A
2
w
w
ꢀ
TG analysis
14
observed in liquid water, but is slightly longer than that of
ꢀ
15
hexagonal or cubic ice (2.76 A). Each O
Fig. 5 illustrates the thermal behaviours of compounds 1 and 2.
Compound 1 possesses excellent thermal stability and is
w
molecule in the
hexamer further forms the hydrogen bonds to the adjacent acy-
lamino O atom of CPTH ligand, making the 3D supramolecular
network of compound 2 more stable.
ꢁ
thermally stable up to around 370 C. Compound 1 underwent
a one-step weight-loss, indicating that both CPTH and phen are
lost simultaneously. The final rescue is proved to be PbO (calcd:
3
7.7%, found: 39.1%). For compound 2, the original weight-loss
Character of CPTH
of ca. 7% in the TG curve of compound 2 is assigned to the loss of
coordinated and lattice water molecules (calcd: 6%). The
ꢁ
CPTH was derived from the hydrothermal in situ acylation
temperature of ca. 390 C for the collapse of the framework is
2 4 2
reaction between BTCA and N H $H O. Based on the acylation
slightly higher than that of compound 1. The remaining is also
PbO, because the calculated value of 57.0% is similar to the
observed one of 56.0%.
reaction mechanism, CPTH should theoretically exhibit a diketo
form (see Scheme 1). But X-ray analysis revealed that two C–O
bond lengths in the complexes are not equal to each other,
indicating that the isomerization for one acylamino group
occurred and CPTH exists in keto-hydroxy form (see Scheme 2).
Table 2 gives the C–O distances of CPTHs in compounds 1 and 2.
When CPTH coordinates to the metal centers, the hydroxyl
group and the carboxyl group deprotonate to balance the metal
charge. So CPTH shows ꢀ2 oxidation state in the complexes.
No examples show that the other acylamino group could also
isomerize into hydroxylimino group. 4-CPTH is really a nice
bridging-mode rigid ligand. In general, CPTH using the carboxyl
Fluorescence property
Fig. 6 gives the fluorescence emission spectra of the title
compounds. Two compounds contain the similar fluorescence
properties with the maximum emission peaks at 468 nm for 1
(lmax ¼ 377 nm) and 466 nm for 2 (lmax ¼ 354 nm). The fluo-
rescence emission should be attributed to the charge transfer of
intra-CPTH ligands, No peaks appear around 365 and 388 nm,
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N H $H O. In the title compounds, 4-CPTH ligand exhibits
2
4
2
four-types of bridging modes. It is noteworthy that 4-CPTH
ligands support the 1D Pb–O ribbons to form a novel 2D layer of
compound 2 with the 1D channels. Both compounds are
potential fluorescence materials.
Acknowledgements
This research was supported by grants from the Basic Research
Foundation of Jilin University (no. 200903133).
Reference
1
(a) A. Mavrandonakis, E. Klontzas, E. Tylianakis and
G. E. Froudakis, J. Am. Chem. Soc., 2009, 131, 13410;
(
3
b) T. Dueren, Y. S. Bae and R. Q. Snurr, Chem. Soc. Rev., 2009,
8, 1237; (c) J. R. Li, R. J. Kuppler and H. C. Zhou, Chem. Soc.
Rev., 2009, 38, 1477; (d) A. C. McKinlay, B. Xiao, D. S. Wragg,
P. S. Wheatley, I. L. Megson and R. E. Morris, J. Am. Chem. Soc.,
Fig. 5 The TG curves of the title compounds.
2008, 130, 10440; (e) T. K. Trung, P. Trens, N. Tanchoux,
S. Bourrelly, P. L. Llewellyn, S. Loera-Sema, C. Serre, T. Loiseau,
F. Fajula and G. F ꢂe rey, J. Am. Chem. Soc., 2008, 130, 16926;
(
f) W. Zhou, H. Wu and T. Yildirim, J. Am. Chem. Soc., 2008, 130,
5268; (g) A. Kuc, T. Heine, G. Seifert and H. A. Duarte, Chem.–
1
Eur. J., 2008, 14, 6597; (h) K. S. Walton, A. R. Millward,
D. Dubbeldam, H. Frost, J. J. Low, O. M. Yaghi and R. Q. Snurr,
J. Am. Chem. Soc., 2008, 130, 406; (i) C. Yang, X. P. Wang and
M. A. Omary, J. Am. Chem. Soc., 2007, 129, 15454; (j) B. Panella,
M. Hirscher, H. Putter and U. Muller, Adv. Funct. Mater., 2006,
1
2
6, 520; (k) J. L. C. Rowsell and O. M. Yaghi, J. Am. Chem. Soc.,
006, 128, 1304; (l) X. B. Zhao, B. Xiao, A. J. Fletcher,
K. M. Thomas, D. Bradshaw and M. J. Rosseinsky, Science, 2004,
06, 1012; (m) A. J. Fletcher, E. J. Cussen, D. Bradshaw,
M. J. Rosseinsky and K. M. Thomas, J. Am. Chem. Soc., 2004,
26, 9750.
3
1
2
3
(a) F. Nouar, J. Eckert, J. F. Eubank, P. Forster and M. Eddaoudi,
J. Am. Chem. Soc., 2009, 131, 2864; (b) Z. Z. Lin, F. L. Jiang,
D. Q. Yuan, L. Chen, Y. F. Zhou and M. C. Hong, Eur. J. Inorg.
Chem., 2005, 1927; (c) A. Deak, T. Tunyogi and G. Palinkas,
J. Am. Chem. Soc., 2009, 131, 2815; (d) L. W. Mi, H. W. Hou,
Z. Y. Song, H. Y. Han, H. Xu, Y. T. Fan and S. W. Ng, Cryst.
Growth Des., 2007, 7, 2553.
(a) P. Horcajada, C. Serre, D. Grosso, C. Boissiere, S. Perruchas,
C. Sanchez and G. F ꢂe rey, Adv. Mater., 2009, 21, 1931;
(
b) D. F. Weng, X. J. Zheng, L. C. Li, W. W. Yang and L. P. Jin,
Dalton Trans., 2007, 4822; (c) A. Rodriguez-Dieguez, S. Galli,
N. Masciocchi, J. M. Gutierrez-Zorrilla, P. Vitoria and E. Colacio,
Dalton Trans., 2007, 1821; (d) J. W. Cheng, S. T. Zheng and
G. Y. Yang, Dalton Trans., 2007, 4059; (e) Y. Q. Sun, J. Zhang and
G. Y. Yang, Chem. Commun., 2006, 4700; (f) B. D. Chandler,
D. T. Cramb and G. K. H. Shimizu, J. Am. Chem. Soc., 2006, 128,
1
0403; (g) D. F. Sun, D. J. Collins, Y. X. Ke, J. L. Zuo and
H. C. Zhou, Chem.–Eur. J., 2006, 12, 3768; (h) J. H. Yu,
X. M. Wang, L. Ye, Q. Hou, Q. F. Yang and J. Q. Xu,
CrystEngComm, 2009, 11, 1037; (i) J. H. Yu, Z. L. L u€ , J. Q. Xu,
H. Y. Bie, J. Lu and X. Zhang, New J. Chem., 2004, 28, 940.
4
5
X. Xue, X. S. Wang, X. Z. You, R. G. Xiong, B. F. Abrahams,
C. M. Che and H. X. Ju, Angew. Chem., Int. Ed., 2002, 41, 2944.
(a) M. Kurmoo, Chem. Soc. Rev., 2009, 38, 1353; (b) K. L. M. Taylor,
W. J. Rieter and W. B. Lin, J. Am. Chem. Soc., 2008, 130, 14358;
(c) X. J. Li, X. Y. Wang, S. Gao and R. Cao, Inorg. Chem., 2006,
45, 1508; (d) Y. Q. Tian, C. X. Cai, X. M. Ren, C. Y. Duan, Y. Xu,
S. Gao and X. Z. You, Chem.–Eur. J., 2003, 9, 5673;
Fig. 6 The fluorescence emission spectra of the title compounds.
indicating that the phen molecule has no contribution to the
16
emission of compound 1.
(
2
e) A. Rodr ´ı guez, R. Kivek €a s and E. Colacio, Chem. Commun.,
005, 5228; (f) T. K. Maji, W. Kaneko, M. Ohba and S. Kitagawa,
Chem. Commun., 2005, 4613; (g) G. Beobide, O. Castillo, A. Luque,
U. Garcia-Couceiro, J. P. Garcia-Teran and P. Roman, Dalton
Trans., 2007, 2669.
Conclusion
In this article, we report the structural characterization of two
layered 4-CPTH-bridged Pb(II) MOFs. 4-CPTH is a new
bridging-mode rigid acylhydrazidate ligand, and derived from
the hydrothermal in situ acylation reaction of 1,2,4-BTCA with
6
(a) D. Farrusseng, S. Aguado and C. Pinel, Angew. Chem., Int. Ed.,
2
009, 48, 7502; (b) L. Q. Ma, C. Abney and W. B. Lin, Chem. Soc.
Rev., 2009, 38, 1248; (c) C. D. Wu and W. B. Lin, Angew. Chem.,
Int. Ed., 2007, 46, 1075; (d) B. Gomez-Lor, E. Gutienez-Puebla,
1
854 | CrystEngComm, 2010, 12, 1850–1855
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View Article Online
M. Iglesias, M. A. Monge, C. Ruiz-Valero and N. Sneiko, Chem.
Mater., 2005, 17, 2568; (e) R. Q. Zou, H. Sakurai and Q. Xu,
Angew. Chem., Int. Ed., 2006, 45, 2542; (f) A. D. Burrows,
C. G. Frost, M. F. Mahon, M. Winsper, C. Richardson,
J. P. Attfield and J. A. Rodgers, Dalton Trans., 2008, 6788;
B. F. Abahams, X. Z. You, Z. L. Xue and C. M. Che, Inorg.
Chem., 2002, 41, 6544; (g) T. Wu, B. H. Yi and D. Li, Inorg. Chem.,
2005, 44, 4130.
10 (a) J. W. Chen, S. T. Zheng and G. Y. Yang, Inorg. Chem., 2008, 47,
4930; (b) Q. Hou, J. H. Yu, J. N. Xu, Q. F. Yang and J. Q. Xu,
CrystEngComm, 2009, 11, 2452; (c) Y. Z. Zhang, M. L. Tong and
X. M. Chen, New J. Chem., 2004, 28, 1412; (d) Q. Hou, J. N. Xu,
J. H. Yu, T. G. Wang, Q. F. Yang and J. Q. Xu, J. Solid State
Chem., 2009, under preparation; (e) B. Masci and P. Thuery, Cryst.
Growth Des., 2008, 8, 1689.
(
g) J. S. Seo, D. Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon and
K. Kim, Nature, 2000, 404, 982; (h) R. Kitaura, G. Onoyama,
H. Sakamoto, R. Matsuda, S. I. Noro and S. Kitagawa, Angew.
Chem., Int. Ed., 2004, 43, 2684; (i) L. G. Qiu, L. N. Gu, G. Hu and
L. D. Zhang, J. Solid State Chem., 2009, 182, 502.
7
8
(a) A. J. Black, N. R. Champness, S. S. M. Chung, W. S. Li and
M. Schr o€ der, Chem. Commun., 1997, 1675; (b) X. M. Zhamg,
Coord. Chem. Rev., 2005, 249, 1201.
(a) X. M. Zhang, M. L. Tong and X. M. Chen, Angew. Chem., Int.
Ed., 2002, 41, 1029; (b) X. M. Zhang, M. L. Tong, M. L. Gong,
H. K. Lee, L. Luo, K. F. Li, Y. P. Tong and X. M. Chen, Chem.–
Eur. J., 2002, 8, 3187; (c) J. Tao, Y. Zhang, M. L. Tong,
X. M. Chem, T. Yuen, C. L. Lin, X. Y. Huang and J. Li, Chem.
Commun., 2002, 1342.
11 (a) J. H. Yu, Y. C. Zhu, D. Wu, Y. Yu, Q. Hou and J. Q. Xu, Dalton
Trans., 2009, 8248; (b) X. X. Hu, J. Q. Xu, P. Cheng, X. Y. Chen,
X. B. Cui, J. F. Song, G. D. Yang and T. G. Wang, Inorg. Chem.,
2004, 43, 2261; (c) F. C. Liu, L. Y. Duan, Y. G. Li, E. B. Wang,
X. L. Wang, C. W. Hu and L. Xu, Inorg. Chim. Acta, 2004, 357, 1355.
12 A. Mizrahi, J.-P. Wignacourt and H. Steinfink, J. Solid State Chem.,
1997, 133, 516.
13 M. V. L oꢂ pez, G. Zaragoza, M. Otero, R. Pedrito, G. Rama and
M. R. Bermejo, Cryst. Growth Des., 2008, 8, 2083.
9
(a) H. Zhao, Z. R. Q u€ , H. Y. Ye and R. G. Xiong, Chem. Soc. Rev.,
14 G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford
University Press, Oxford, 1997.
15 (a) D. Eisenberg, W. Kauzmann, The Structure and Properties of
Water, Clarendon Press, Oxford, 1969, p. 71; (b) N. H. Fletcher,
The Chemical Physics of Ice, Cambridge University Press,
Cambridge, 1970.
2
008, 37, 84; (b) R. G. Xiong, X. Xue, H. Zhao, X. Z. You,
B. F. Abrahams and Z. L. Xue, Angew. Chem., Int. Ed., 2002, 41,
800; (c) J. Tao, Z. J. Ma, R. B. Huang and L. S. Zheng, Inorg.
3
Chem., 2004, 43, 6133; (d) L. Z. Wang, Z. R. Q u€ , H. Zhao,
X. S. Wang, R. G. Xiong and Z. L. Xue, Inorg. Chem., 2003, 42,
3
969; (e) X. S. Wang, Y. Z. Tang, X. F. Huang, Z. R. Q u€ ,
C. M. Che, P. W. H. Chan and R. G. Xiong, Inorg. Chem., 2005,
4, 5278; (f) X. Xue, X. S. Wang, L. Z. Wang, R. G. Xiong,
16 X. Shi, G. S. Zhu, Q. R. Fang, G. Wu, G. Tian, R. W. Wang,
D. L. Zhang, M. Xue and S. L. Qiu, Eur. J. Inorg. Chem., 2004,
185.
4
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