Six new metal-organic frameworks based on polycarboxylate acids and V-shaped imidazole-based synthon: Syntheses, crystal structures, and properties

Article abstract of DOI:10.1021/ic102207n

Solvothermal reactions of 4,4′-bis(imidazol-1-yl)diphenyl ether (BIDPE) with deprotonated 5-hydroxy-isophthalic acid (5-OH-H₂bdc), and benzene-1,3,5-tricarboxylic acid (H₃btc) in the presence of cadmium(II), zinc(II), cobalt(II), nic

Full text of DOI:10.1021/ic102207n

ARTICLE
pubs.acs.org/IC
Six New Metal-Organic Frameworks Based on Polycarboxylate Acids
and V-shaped Imidazole-Based Synthon: Syntheses,
Crystal Structures, and Properties
Jinsong Hu,† Liangfang Huang,† Xiaoqiang Yao,† Ling Qin,† Yizhi Li,† Zijian Guo,† Hegen Zheng,*,†,‡ and
Ziling Xue*,§
†State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of
Microstructures, Nanjing University, Nanjing 210093, People’s Republic of China
‡State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou 350002, People’s Republic of China
§Department of Chemistry, The University of Tennessee, Knoxville, Tennessee 37996-1600, United States
S Supporting Information
b
ABSTRACT: Solvothermal reactions of 4,40-bis(imidazol-1-yl)diphenyl ether (BIDPE) with deprotonated 5-hydroxy-isophthalic
acid (5-OH-H2bdc), and benzene-1,3,5-tricarboxylic acid (H3btc) in the presence of cadmium(II), zinc(II), cobalt(II), nickel(II),
and manganese(II) salts in H2O or H2O/DMF produced six new complexes, namely, [Cd(BIDPE)(5-OH-bdc) H2O]n (1),
3
[Co(BIDPE)(5-OH-bdc) H2O]n (2), [Zn3(BIDPE)3(5-OH-bdc)3 4H2O]n (3), [Ni(BIDPE)2(5-OH-bdc)(H2O) 3H2O]n (4),
3
3
3
{[Mn2(BIDPE)2(5-OH-bdc)2]n (5), and [Ni(BIDPE)2(Hbtc)(H2O)]n (6). These complexes were characterized by elemental
analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1 and 2 reveal the same two-dimensional (2D) sheets
with a 32-membered [(Cd/Co)2(BIDPE)2] metallocyclic ring constructed from BIDPE and 5-OH-H2bdc with Cd or Co salts. For
compound 3, six identical 2D sheets are polycatenated in parallel to form a rare 2D f 2D framework; it displays ferroelectric
behavior with a remnant electric polarization (Pr) of 0.033 μC/cm2 and an electric coercive field (Ec) of 11.15 kV/cm. In
compounds 4 and 6, only one carboxyl group coordinated to the Ni atom from 5-OH-H2bdc or H3btc. Compound 5 exists as
binuclear Mn clusters, which are linked by BIDPE and 5-OH-H2bdc to generate a 2D sheet and displays weak antiferromagnetic
character. In addition, the thermal stabilities and photochemical properties of these new complexes have been studied.
’ INTRODUCTION
Excellent coordination ability and free rotation of the imidazole
ring in multidentate ligands meet the requirement of coordina-
tion geometries of metal ions in the assembly process. Until now,
a great number of ingenious MOFs have been designed based on
imidazole ligands.12 We recently designed and synthesized 4,40-
bis(imidazol-1-yl) diphenyl ether (BIDPE, Scheme 1), which is a
V-shaped imidazole ligand that can be regarded as a half-flexible
ligand.13 The H3btc and 5-OH-H2bdc are V-shaped or triangular
ligands, which have some connects in structures. To test the
ability of this ligand to give new architectures and topologies, we
selected this ligand, 5-OH-H2bdc, H3btc (Scheme 1), and different
bivalent metal salts to solvothermally synthesize six new coordi-
nation polymers with intriguing structures, namely, [Cd(BIDPE)
(5-OH-bdc) H2O]n (1), [Co(BIDPE)(5-OH-bdc) H2O]n (2),
The designed construction of metal-organic frameworks
(MOFs) from various molecular building blocks connected by
coordination bond, supramolecular contacts, has been of intense
interest, because of their intriguing aesthetic structures and
topological features,1 as well as their promising applications in
photochemistry areas,2 molecular magnetism,3 heterogeneous
catalysis,4 and molecular sorption.5 However, it is still a great
challenge to rationally design and construct the desired com-
pounds. Many factors, such as organic ligands,6 solvent system,7
metal ions,8 and counterions,9 are found to greatly influence the
structures, rendering it difficult to predict the construction of
molecular architectures. Therefore, systematic studies of diversi-
fied conditions leading to different structures in the formation of
coordination polymers are important and of intense interest.
Recently, a large number of mixed-ligand MOFs have been
reported,10 revealing that the combination of different ligands
can result in greater tunability of structural frameworks than
single ligands. Therefore, mixed ligands are a good choice for the
construction of new polymeric structures.
3
3
[Zn3(BIDPE)3(5-OH-bdc)3 4H2O]n (3), [Ni(BIDPE)2(5-OH-
3
bdc)(H2O) 3H2O]n (4), {[Mn2(BIDPE)2(5-OH-bdc)2]n (5),
3
and [Ni(BIDPE)2(Hbtc)(H2O)]n (6). Thenewcompoundshave
been characterized by elemental analysis, IR spectra, and X-ray
crystallography. The crystal structures, topological analyses,
and their thermal properties have been studied. In addition,
Several N-donor ligands have been widely employed to
construct coordination polymers with fascinating architectures
and interesting properties.11 Among the N-donor ligands, multi-
dentate ligands with imidazole groups have attracted great interest.
Received: November 2, 2010
Published: February 08, 2011
r
2011 American Chemical Society
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Scheme 1. The V-shaped Imidazole Ligand and Polycarboxylate Ligands
Table 1. Crystallographic Data for Complexes 1-6
1
2
3
4
5
6
formula
formula weight
crystal system
space group
a (Å)
C26H20O7N4Cd C26H20O7N4Co C78H62O22N12Zn3 C44H40O11N8Ni C52H36O12N8Mn2 C45H36N8O9Ni
612.87
559.39
1705.55
orthorhombic
Fdd2
915.53
1074.66
monoclinic
P21/c
891.50
monoclinic
P21/n
monoclinic
P21/n
monoclinic
C2/c
monoclinic
P21/c
9.5126(10)
24.370(3)
11.7544(12)
90.00
9.1980(10)
24.288(3)
11.4782(12)
90.00
25.498(5)
30.011(6)
44.331(9)
90.00
26.548(2)
10.1451(8)
30.495(2)
90.00
11.7405(10)
19.0544(18)
19.8722(18)
90.00
8.5856(12)
18.375(3)
24.508(3)
90.00
b (Å)
c (Å)
R (deg)
β (deg)
γ (deg)
V (Å3)
111.403(2)
90.00
108.909(2)
90.00
90.00
102.028(2)
90.00
97.039(2)
90.00
90.730(3)
90.00
90.00
2537.0(5)
4
2425.9(5)
4
33923(12)
16
8033.0(11)
100
4412.1(7)
4
3866.1(10)
4
Z
Dc (g cm-3
)
1.605
1.532
1.329
1.514
1.618
1828
μ(Mo) KR (mm-1
)
0.914
0.763
0.917
0.559
0.653
0.575
F(000)
1232.0
1148
13920
3808
2200
2216
theta min-max (deg)
tot., uniq. data
R(int)
2.04, 25.00
12515
1.68, 25.00
11966
2.10, 25.00
41244
2.29, 25.00
19378
2.05, 25.00
21724
1.66, 25.00
19051
0.0317
0.0454
0.0523
0.0541
0.0572
0.0448
observed data [I > 2σ(I)] [I > 2σ(I)] 3948
3060
9877
4748
5620
5247
R1, wR2 [I > 2σ(I)]
0.0450, 0.1290
0.0585, 0.1478
1.011
0.0749, 0.1824
0.966
0.0531, 0.1196
0.975
0.0481, 0.0858
0.965
0.0430, 0.0940
0.994
S
1.095
min. and max. Resdens (e Å-3
)
-0.894, 1.138
-0.630, 0.972
-0.854, 1.944
-0.573, 0.655
-0.289, 0.361
-0.398, 0.436
photoluminescences, ferroelectric behavior, and magnetic char-
acter for complexes 1-6 are discussed in detail.
characterized by thermogravimetric analysis (TGA) on a Perkin-Elmer
thermogravimetric analyzer Pyris 1 TGA up to 1023 K, using a heating
rate of 10 K min-1 under N2 atmosphere. Temperature-dependent
magnetic susceptibility data were obtained on a MPMS XL-7 SQUID
magnetometer under an applied field of 2000 Oe over the temperature
range of 2-300 K.
’ EXPERIMENTAL SECTION
Materials and Methods. The reagents and solvents employed
were commercially available and used as received. BIDPE was prepared
by the literature methods.13 IR absorption spectra of the complexes was
recorded in the range of 400-4000 cm-1 on a Nicolet (Impact 410)
spectrometer with KBr pellets (5 mg of sample in 500 mg of KBr). C, H,
and N analyses were carried out with a Perkin-Elmer 240C elemental
analyzer. Powder X-ray diffraction (PXRD) measurements were per-
formed on a Bruker D8 Advance X-ray diffractometer using Cu KR
radiation (λ = 1.5418 Å), in which the X-ray tube was operated at 40 kV
and 40 mA. Solid-state UV-vis diffuse reflectance spectra was obtained
at room temperature using a Shimadzu UV-3600 double monochroma-
tor spectrophotometer, and BaSO4 was used as a 100% reflectance
standard for all materials. Luminescent spectra were recorded with a
Shimadzu VF-320 X-ray fluorescence spectrophotometer at room tem-
perature. The emission decay lifetimes were measured on an Edinburgh
Instruments FLS920 fluorescence spectrometer. The electric hysteresis
loops were recorded on a Ferroelectric Tester Precision Premier II made
by Radiant Technologies, Inc. The as-synthesized samples were
Syntheses of the Compounds. [Cd(BIDPE)(5-OH-bdc) H2O]n
3
(1). A mixture of Cd(NO3)2 4H2O (30.1 mg, 0.1 mmol), 5-OH-H2bdc
3
(18.2 mg, 0.1 mmol) and BIDPE (28.4 mg, 0.1 mmol) was dissolved in
9 mL of DMF/H2O(2:1, v/v). The final mixture was placed in a Parr
Teflon-lined stainless steel vessel (15 mL) under autogenous pressure
and heated at 90 °C for 3 d. A large quantity of colorless-plank crystals
were obtained, which were washed with mother liquid, and dried under
ambient conditions (yield: 73%, based on BIDPE). Anal. Calcd for
C26H20O7N4Cd: C, 50.95, H, 3.29, N, 9.14; found C, 50.87, H, 3.31, N,
9.26. IR (KBr, cm-1): 3456(w), 3115(w), 1554(s), 1518(s), 1383(s),
1240(s), 1123(m), 1067(s), 1015(w), 964(w), 930(w), 855(m), 824(s),
745(s), 653(m), 531(m).
[Co(BIDPE)(5-OH-bdc) H2O]n (2). Compound 2 was prepared by
3
a procedure similar to that for the preparation of compound 1, using
Co(NO3)2 6H2O (29.1 mg, 0.1 mmol), 5-OH-H2bdc (18.2 mg, 0.1
3
mmol), and BIDPE (30.2 mg, 0.1 mmol) in 9 mL DMF/H2O (1:2, v/v).
Purple crystals were obtained (yield: 66%, based on BIDPE). Anal.
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Scheme 2. Crystallographically Established Coordination Modes of Carboxylic Groups in Compounds 1-6
Figure 1. (a) Coordination environment of the Cd(II) ion in 1. The hydrogen atoms are omitted for clarity. Symmetry codes: (#1) 0.5 þ x, 0.5 - y, -
0.5 þ z; (#2) -x, -y, 2 - z. (b) Views of the 2D sheet by BIDPE ligands, 5-OH-bdc2- and Cd(II) ions. (c) Views of the 2D sheets with ABAB stack.
(d) Schematic representation of 2D sheets of compound 1 with ABAB stack.
Calcd for C26H20O7N4Co: C, 55.82, H 3.60, N, 10.02; found C, 55.73,
H, 3.71, N, 9.94. IR (KBr, cm-1): 3406(m), 3156(w), 2353(w), 1613(m),
1537(s), 1518(s), 1497(s), 1394(w), 1247(s), 1121(m), 1069(s),
966(w), 942(w), 839(m), 812(w), 772(s), 734(s), 656 (m), 526(m).
[Ni(BIDPE)2(5-OH-bdc)(H2O) 3H2O]n (4). A mixture of Ni(NO3)2
3
3
6H2O (29.1 mg, 0.1 mmol), 5-OH-H2bdc (18.2 mg, 0.1 mmol) and
BIDPE (30.2 mg, 0.1 mmol) was added to 10 mL of H2O, and the pH
was adjusted to 7.0 via the addition of 1 M NaOH solution. The final
mixture was placed in a Parr Teflon-lined stainless steel vessel (15 mL)
under autogenous pressure and heated at 130 °C for 2 d. Green crys-
tals were obtained (yield: 66%, based on BIDPE). Anal. Calcd for
C44H40O11N8Ni: C, 57.72, H 4.40, N, 12.24; found C, 57.64, H, 4.51, N,
12.30. IR (KBr, cm-1): 3261(w), 3095(w), 1609(m), 1563(s), 1514(s),
1390(m), 1344(s), 1265(m), 1237(s), 1167(m), 1122(m), 1066(s),
964(m), 936(m), 853(w), 834(m), 732(m), 711(m), 661(m), 534(m).
[Mn2(BIDPE)2(5-OH-bdc)2]n (5). Compound 5 was prepared by a
procedure similar to that for the preparation of compound 4, using
[Zn3(BIDPE)3(5-OH-bdc)3 4H2O]n (3). Compound 3 was prepared
3
by a procedure similar to that for the preparation of compound 1, using
Zn(NO3)2 6H2O (29.7 mg, 0.1 mmol), 5-OH-H2bdc (18.2 mg, 0.1
3
mmol) and BIDPE (28.4 mg, 0.1 mmol). A large quanitity of colorless-
plank crystals were obtained (yield: 53%, based on BIDPE). Calcd for
C78H62O22N12Zn3: C, 54.61, H 3.64, N, 9.80; found C, 54.48, H, 3.74, N
9.96. IR (KBr, cm-1): 3406(m), 3157(s), 1618(m), 1556(s), 1520(s),
1498(m), 1369(s), 1273(m), 1243(s), 1124(m), 1066(m), 966(m),
942(m), 836(w), 776(m), 567(m), 527(m).
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’ RESULTS AND DISCUSSION
Crystal Structure of [Cd(BIDPE)(5-OH-bdc) H2O]n (1). X-
3
ray analysis reveals that 1 crystallized in monoclinic space group
P21/n. The asymmetric unit of 1 contains an independent Cd(II)
cation, one 5-OH-bdc2- anion, one BIDPE ligand, and one
lattice water molecule. As shown in Figure 1a, the Cd(II) center
is 6-coordinated by four carboxylic O atoms from two 5-OH-
H2bdc ligands and two nitrogen atoms from two BIDPE ligands
to form a distorted octahedral geometry. The Cd-O lengths are
in the range of 2.212(3)-2.587(3) Å and Cd-N lengths are
2.238(4)-2.253(4) Å, which are all similar to the values found in
other Cd(II) complexes.16
Two BIDPE ligands connect two Cd(II) atoms to achieve a
32-membered [Cd2(BIDPE)2] metallocyclic ring exhibiting max-
imum dimension of (corresponding to the Cd Cd distance
3 3 3
and O O separation) 16.156 Å ꢀ 8.507 Å, and the N1-Cd-
3 3 3
Figure 2. Coordination environment of the Co(II) ion in 2. The
hydrogen atoms are omitted for clarity. Symmetry codes: (#1) 0.5 þ
x, 1.5 - y, -0.5 þ x; (#2) 1 - x, 1 - y, 2 - z.
N4 angle is 96.01(15)°. Each completely deprotonated 5-OH-
bdc2-anion coordinates to two Cd atoms by adopting chelating
bidentate coordination modes (Scheme 2a). The extension of
the structure into a 2D sheet is accomplished by 5-OH-bdc2-
anions linking the [Cd2(BIDPE)2] loops, as shown in Figure 1b.
Each Cd atom is connected to three others via two 5-OH-bdc2-
and two BIDPE ligands which all can be regarded as two connected
linkers. In this analysis, the network topology features a 3-con-
nected (6,3) net. As a result of the geometric characteristics of
this two-dimensional (2D) sheet, the loops and the 2D layer are
not in a plane, parts of BIDPE ligands can protrude into the
cavities of the adjacent sheets, and the adjacent layers are stacked
in an offset ABAB manner (Figure 1c and 1d).
MnCl2 4H2O (19.8 mg, 0.1 mmol), 5-OH-H2bdc (18.2 mg, 0.1 mmol)
3
and BIDPE (30.2 mg, 0.1 mmol) in 10 mL of H2O, and the pH was
adjust to 7.0 via the addition of 1 M NaOH solution. The final mixture
was placed in a Parr Teflon-lined stainless steel vessel (15 mL) under
autogenous pressure and heated at 110 °C for 2 d. A large quantitiy of
pale yellow crystals were obtained (yield: ca. 46%, based on BIDPE).
Anal. Calcd for C52H36O12N8Mn2: C, 58.11, H 3.38, N, 10.43; found C,
58.19, H, 3.21, N, 10.40. IR (KBr, cm-1): 3248(w), 3136(w), 1617(m),
1549(s), 1513(s), 1420(m), 1378(s), 1266(s), 1241(s), 1167(m),
1122(m), 1066(s), 970(w), 926(w), 881(m), 820(m), 732(m), 711(m),
661(m), 534(m).
Crystal Structure of [Co(BIDPE)(5-OH-bdc) H2O]n (2). The
3
coordination environment of 2 is a slightly different from that of
1: Co(II) lies in a distorted trigonal bipyramidal coordination
environment of three carboxylic O atoms from two 5-OH-bdc2-
ligands and two nitrogen atoms from two BIDPE ligands (Figure 2).
Carboxyl groups of 5-OH-bdc2- adopt two coordination modes:
one carboxyl group adopts a monodentate coordination mode,
whereas another carboxyl group coordinates to the same Co
center by adopting a chelating coordination mode (Scheme 2b).
Because the structure is very similar to that of compound 1, we do
not describe it any further.
[Ni(BIDPE)2(Hbtc)(H2O)]n (6). A mixture of Ni(NO3)2 6H2O (29.7
3
mg, 0.1 mmol), H3btc (10.5 mg, 0.05 mmol), and BIDPE (30.2 mg, 0.1
mmol) was added to 10 mL of H2O, and the pH was adjusted to 6.0 via
the addition of 1 M NaOH solution. The final mixture was placed in a
Parr Teflon-lined stainless steel vessel (15 mL) under autogenous pre-
ssure and heated at 130 °C for 3 d. Green crystals were obtained (yield:
45%, based on BIDPE). Anal. Calcd for C45H34O9N8Ni: C, 60.76, H
3.85, N, 12.60; found C, 60.68, H, 3.77, N 12.71. IR (KBr, cm-1):
3134(w), 3075(w), 1685(s), 1634(s), 1602(w), 1553(s), 1512(s),
1448(m), 1375(s), 1268(s), 1240(s), 1128(w), 1103(m), 1064(m),
963(w), 938(w), 877(m), 836(w), 798(m), 760(s), 722(m), 663(m),
523(m).
Crystal Structure of [Zn3(BIDPE)3(5-OH-bdc)3 4H2O]n
3
(3). X-ray analysis reveals that compound 3 is solved in ortho-
rhombic space group Fdd2. The fundamental building unit of 3
contains three independent Zn(II) cations, three 5-OH-bdc2-
anions, three BIDPE ligands, and four free water molecules.
The 5-OH-bdc2- ions take the coordination modes 2b and 2c
(Scheme 2). As shown in Figure 3a, Zn1(II) and Zn3(II) are
4-coordinated by two carboxylic O atoms from two 5-OH-H2bdc
and two nitrogen atoms from two BIDPE ligands to form a dis-
torted tetrahedral geometry, whereas the Zn2(II) is in an octa-
hedral coordination environment of four carboxylic O atoms
from two 5-OH-H2bdc and two nitrogen atoms from two BIDPE
ligands. The Zn-O lengths are in the range of 1.968(4)-
2.488(5) Å and the Zn-N lengths are 1.972(5)-2.048(6) Å, which
are all similar to the values found in other Zn(II) complexes.17
5-OH-bdc2- anions link neighboring Zn(II) ions to form an infi-
X-ray Crystallography. Single crystals of 1-6 were prepared by
the methods described in the synthetic procedure. X-ray crystallographic
data of 1-6 were collected at room temperature using epoxy-coated
crystals mounted on glass fiber. All measurements were made on a Bruker
Apex Smart CCD diffractometer with graphite-monochromated Mo KR
radiation (λ = 0.71073 Å). The structures of complexes 1-6 were solved
via 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 procedures based on F2 values.14 The hydrogen
atom positions were fixed geometrically at calculated distances and
allowed to ride on the parent atoms. The distribution of peaks in the
channels of 3 was chemically featureless to refine, using conventional
discrete-atom models. To resolve these issues, the contribution of the
electron density by the remaining solvent molecules were removed by
the SQUEEZE routine in PLATON.15 The numbers of solvent mole-
cules in 3 were obtained by element analysis and thermogravimetric
analysis. The relevant crystallographic data are presented in Table 1,
while the selected bond lengths and angles are given in Table S1 in the
Supporting Information.
nitely 1D zigzag chain. The Zn Zn distances are 9.556-9.938 Å.
3 3 3
The BIDPE ligands link these zigzag chains to form a wavelike 2D
sheet (Figure 3b). In this sheet, each 4-membered cycle is formed by
four Zn(II) ions, two 5-OH-bdc2- anions, and two BIDPE ligands.
The 2D sheet contains a larger channel (for the sake of clarity, the
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Figure 3. (a) Coordination environment of the Zn(II) ions in 3. The hydrogen atoms are omitted for clarity. Symmetry codes: (#1) 0.25 - x, -0.25 þ
y, -0.25 þ z; (#2) x, 1 þ y, z; (#3) 0.25 - x, 0.75 þ y, -0.25 þ z; (#4) 0.25 - x, 0.25 þ y, 0.25 þ z. (b) Views of the wavelike 2D framework by 5-OH-
bdc2-, BIDPE, and Zn ions along the a-axis. (c) Views of the reduced wavelike 2D framework in different directions. (d) Schematic representation of the
2D f 2D framework by six identical sheets.
purple rod was added), the size is ∼15.633 Å ꢀ 12.511 Å. The
Zn(II) ions can be regarded as 4-connected nodes with all crystal-
lographically independent 5-OH-bdc2- ligands acting as 2-con-
nected linkers, and BIDPE ligands acting as V-shaped linkers. There-
fore, the entire structure can be reduced as a (4,4) sheet (Figure 3c).
The large channel within each sheet allows them to interpenetrate
between the adjacent sheets in a “parallel interpenetration” fashion,
resulting in a finite polycatenation. By analysis, only six of these
identical sheets are polycatenated (Figure 3d).
To the best of our knowledge, among the known 2D interpene-
trating polymers, most of the studies have focused on the 3-connected
(6,3) or (4,4) networks, because of their large voids. The most
examples are the mode of 2D f 2D interpenetration by adjacent nets
or 2D f 3D polycatenation by infinite nets. However, finite identical
networks (>3) polycatenated were rarely reported, as evidenced in a
review by Batten and Ciani.18 As we know, this is the first report of six
identical sheets polycatenated still to form a 2D f 2D network.
Crystal Structure of [Ni(BIDPE)2(5-OH-bdc)(H2O) 3H2O]n
3
(4). The asymmetric unit of 4 contains one Ni(II) cation, one
5-OH-bdc2- anion, one BIDPE ligand, one coordinated water
molecule, and three lattice water molecules. The 5-OH-H2bdc
ligands take the coordination mode: one carboxyl group has
monodentate coordination, and another is deprotonated as an
anion (Scheme 2d). As shown in Figure 4a, each Ni(II) atom is
six-coordinated by four N atoms from four BIDPE ligands, two O
atoms from 5-OH-bdc2- anion and coordinated water molecule.
The Ni-O lengths are 2.087(2)-2.102(2) Å and the Ni-N
lengths are 2.082(3)-2.138(3) Å, which are similar to those
found in other Ni(II) complexes.19
The neighboring Ni(II) ions are linked by BIDPE ligands and
5-OH-bdc2- anions to form infinitely double-stranded 1D chain.
The adjacent distance of Ni Ni is 15.258 Å. Two BIDPE
3 3 3
ligands connect two Ni(II) atoms to achieve a 32-membered [Ni2-
(BIDPE)2] metallocyclic ring exhibiting maximum dimensions
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Figure 4. (a) Coordination environment of the Ni(II) ion in 4. The hydrogen atoms are omitted for clarity. Symmetry codes: (#1) x, -y, 0.5 þ z; (#2) x,
-y, -0.5 þ z. (b) Views of the 1D double-stranded chain by 5-OH-bdc2- and Ni ions. (c) Views of the 3D network formed by hydrogen bondings.
of (corresponding to the Ni Ni distance and O
O
monodentate coordination mode (Scheme 2e and 2f). The Mn1-
(II) is in an octahedral coordination geometry coordinated by
two nitrogen atoms from two BIDPE ligands (Mn1-N:
2.220(2)-2.229(2) Å) in the apical positions and four oxygen
atoms from three 5-OH-bdc2- anions (Mn1-O: 2.108(2)-
2.530(2) Å) in the equatorial positions. The Mn2(II) is five
coordinated by two nitrogen atoms from two BIDPE ligands
(Mn2-N: 2.225(2)-2.244(2) Å) and three oxygen atoms from
three 5-OH-bdc2- anions (Mn2-O: 2.111(2)-2.149(2) Å).
In compound 5, the Mn(II) atoms were bridged by carbox-
3 3 3
3 3 3
separation) 15.258 Å ꢀ 10.120 Å. The angles of N3-Ni-N5
and N1-Ni-N8 are 91.626(1)° and 93.389(1)°, respectively. In
each 5-OH-bdc2- anion, only one carboxyl group coordinates to
Ni atom, whereas another is deprotonated and acts as a coun-
teranion (Figure 4b). Further inspection shows that the coordi-
nated water, lattice water, carboxyl groups, and hydroxyl groups
are actually contacting each other by strong hydrogen bonding
(O O distances range from 2.697 to 3.036 Å) (see Table S2 in
3 3 3
the Supporting Information). These hydrogen bonds are com-
posed of two parts: one contains coordinated water, lattice water,
and carboxyl groups, whereas another is composed of hydroxyl
groups and carboxyl groups (Figure 4c). Obviously, these hydro-
gen-bonded interactions are also available to increase the stability
of the entire crystal structure of 4. This extension of the structure
into a three-dimensional (3D) framework is accomplished via
hydrogen-bonded interactions.
ylate ligands to form an binuclear cluster with Mn Mn sep-
3 3 3
aration of 4.922(3) Å. Each binuclear Mn was connected by four
5-OH-bdc2- anions to form a 1D ladder-shaped chain (Figure 5b).
The BIDPE ligands share the binuclear Mn clusters with 5-OH-
bdc2- anions to further generate an infinite 2D network (Figure 5c).
In this network, each two BIDPE ligands linked two binuclear
Mn clusters in a parallel fashion (Figure 5d). A better insight into
the nature of this network can be achieved by the application of a
topological approach. The binuclear Mn cluster can be regarded
as 4-connected nodes with all crystallographically independent
BIDPE ligands and 5-OH-bdc2- acting as 2-connected linkers.
Therefore, the entire structure can be represented as a (4,4) sheet
topology (Figure 5e).
Crystal Structure of [Mn2(BIDPE)2(5-OH-bdc)2]n (5). When
Ni(NO3)2 was replaced by MnCl2, a structurally different com-
plex 5 was obtained. As shown in Figure 5a, 5 is consists of two
crystallographically independent Mn(II) ions, two BIDPE li-
gands, and two 5-OH-bdc2- anions. The 5-OH-bdc2- anions
adopt three coordination modes. One carboxyl group adopts a
bismonodentate coordination mode to bridge two Mn centers,
one carboxylate group coordinates to the same Mn center by
adopting a chelating coordination mode, and the other adopts
Crystal Structure of [Ni(BIDPE)2(Hbtc)(H2O)]n (6). The
crystal structure of 6 was solved in the space group P21/c. As
depicted in Figure 6a, the structure contains one crystallographically
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Figure 5. (a) Coordination environment of the Mn(II) ion in 1. The hydrogen atoms are omitted for clarity. Symmetry codes: (#1) 1 þ x, 1.5 - y, -0.5
þ z; (#2) -1 þ x, 1.5 - y, 0.5 þ z; (#3) x, 1.5 - y, 0.5 þ z; (#4) x, 1.5 - y, -0.5 þ z. (b) Views of the 1D trapezoidal chain by bdc2- and Mn ions along
the b-axis. (c) Views of the 2D network. (d) Each two BIDPE ligands linked two binuclear Mn clusters in parallel fashion. (e) Schematic representation of
the (4,4) sheet.
independent Ni(II) ion, two BIDPE ligands, one Hbtc2- anion,
and one coordinated water molecule. In 6, the H3btc displays an
unusual mode of coordination, with only two carboxyl groups
deprotonated: one carboxyl group coordinates to the Ni atom,
and another acts as the counteranion (Scheme 2g). The Ni(II) ions
has a disordered octahedral geometry with one carboxylic O
atom from a Hbtc2- anion, one coordinated water in the axial
position, and four nitrogen atoms from four BIDPE ligands in the
equatorial plane. The Ni-O lengths are 2.065(3)-2.148(2) Å
and the Ni-N lengths are 2.091(2)-2.114(2) Å.
In compound 6, each Ni atom is connected by BIDPE, H3btc,
and coordinated water to form a 2D puckered sheet. In the sheet,
the four BIDPE ligands and four Ni atoms afford a square with a
large window of 16.221 Å ꢀ 16.067 Å. The Hbtc2- and water
molecule share a Ni atom and fill in the grids (Figure 6b).
Because of the spacious nature of a single sheet, it allows another
identical sheet to interlock with it, leading to a 2-fold interlocked
structure (Figures 6c and 6e). These interlocked double sheets
(red and green) are packed in an offset fashion. There are strong
(O-H O) hydrogen bonds (the O O distance is 2.611 Å)
3 3 3
3 3 3
between the interlocked sheets, which involve the coordinated
water from one sheet and the carboxyl groups from another
sheet, and vice versa. Similarly, these identical sheets (red or
green) also exist as strong hydrogen bonds (the O O distance
3 3 3
is 2.612 Å) formed by carboxyl groups among the sheets (see
Table S3 in the Supporting Information). These hydrogen bonds
change the framework from 2D to 3D (Figure 6d). Obviously,
these hydrogen-bonded interactions increase the stability of the
entire crystal structure of 6, because it does not decompose until
390 °C. This suggests that carboxyl group and coordinated water
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Figure 6. (a) Coordination environment of the Ni(II) ion in 6. The hydrogen atoms are omitted for clarity. Symmetry codes: (#1) 1 - x, -0.5 þ y, -
0.5 - z; (#2) 3 - x, 0.5 þ y, 0.5 - z. (b) Views of the 2D puckered sheet along the a-axis. (c, d) Views of the 3D network formed by hydrogen bondings.
(e) Schematic representation of the 2-fold interlocked sheets.
play an important role in increasing the dimension and sustaining
the stabilization of the entire structure.
Table 2. Different Angles of BIDPE Ligand
compound
angle (N Ocore N)
3 3 3 3 3 3
Compounds 1-6 have various structures; the results have
shown that the different structures are evidently affected by the
configuration of BIDPE. It can slightly adjust the angles to meet
the requirement of coordination. The angles can be assessed by
comparing the N Ocore N angle defined by the central
1
2
3
4
5
6
124.088°
124.928°
130.165°, 128.619°, 132.272°
114.206°, 115.522°
128.191°, 127.784°
138.853°, 132.810°
3 3 3
3 3 3
oxygen atom and the coordinated nitrogen atoms of the imida-
zole groups. To illuminate the influence of the angles, the angles
are listed in Table 2. From these, we can know that BIDPE can
adjust the corresponding angles from 114.206° to 138.853° to
meet the requirement of coordination; when coordinated with
5-OH-H2bdc, the angles are smaller than that coordinated with
H3btc (the angle is up to 138.853°). It is undoubtedly an ideal
half-flexible N-containing ligand.
2.94%) is observed from 50 °C to 155 °C, which is attributed to the
loss of the lattice water, and the structure was decomposes starting at
388 °C. In the case of 2, a weight loss is observed from 20 °C to
160 °C, which is attributed to the release of the lattice water with a
weight loss of 3.04% (calcd 3.22%), and then the network collapses
at 400 °C. Compound 3 experienced a weight loss of 4.21% (calcd
4.12%) from 20 °C to 150 °C, which is attributed to the loss of four
lattice water molecules, and the framework collapses at 390 °C. For
Thermal Analysis and XRD Results. To characterize the
complexes more fully, in terms of thermal stability, their thermal
behaviors were studied by TGA (see Figure S5 in the Supporting
Information). For complex 1, a rapid weight loss of 2.71% (calcd
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various atoms, enhancing the “rigidity” of the ligands and re-
ducing the loss of energy by radiationless decay.20 In addition, the
UV-vis absorption spectra of compounds 1, 2, 3, 4, and 6 were
carried out in the crystalline state at room temperature (BIDPE
and 5-OH-H2bdc in solid state). As shown in Figure S2 in the
Supporting Information, BIDPE and 5-OH-H2bdc show intense
absorption peaks at 220-340 nm, which can be ascribed to π-
π* transitions of the ligands. Energy bands of complex 2 from
500-600 nm, of complex 4 from 550-640 nm and 360-390 nm,
and of complex 6 from 630-700 nm and 380-420 nm, are
assigned as d-d transitions, while lower energy bands from
310-340 nm are probably assigned as metal-to-ligand charge-
transfer (MLCT) transitions. These characteristic bands in this
range do not appear in the spectra of the Cd2þ, Zn2þ complexes
(see Figure S2 in the Supporting Information). A possible
explanation for Cd2þ and Zn2þ could be found in their 3d10
electronic states, which are more stable.21 Furthermore, the
emission decay lifetimes of compounds 1 and 3 were monitored
and the curves are best fitted by biexponentials in the solid.22
The emission decay lifetimes of the compounds 1 and 3 are as
follows: complex 1, τ1 = 4.455 ns (19.85%) and τ2 = 1.132 ns
(80.15%) (χ2 = 1.072, see Figure S3 in the Supporting
Information); complex 3, τ1 = 1.729 ns (28.68%) and τ2 =
3.991 ns (71.32%) (χ2 = 1.196, see Figure S4 in the Supporting
Information).
Figure 7. Polarization versus applied electric field curve (electric
hysteresis loop of a powder pellet) of 3.
Ferroelectric Property of Complex 3. Complex 3 crystal-
lizes in a noncentrosymmetric space groups (fdd2), which is
associated with the point groups of C2v, one of the 10 polar
point groups (C1, Cm, C2, C2v, C3, C3v, C4, C4v, C6, C6v) may
have the potential to display ferroelectric behavior; thus, the
ferroelectric feature was investigated. The electrical hysteresis
loop of complex 3 was recorded at room temperature, using
powdered samples in pellets.23 Experimental results indicate
the presence of electric hysteresis loops with a remnant electric
polarization (Pr) of 0.033 μC/cm2 and an electric coercive field
(Ec) of 11.15 kV/cm; the spontaneous saturation polarization
(Ps) of complex 3 is ca. 0.105 μC/cm2 (Figure 7), which is
smaller than that of Zn powder sample [Zn(1,3-bibm)(D-ca)]n
(Pr = 0.052 μC/cm2, Ps = 0.143 μC/cm2) and larger than
[Zn(1,4-bibm)(D-ca)]n (Pr = 0.022 μC/cm2, Ps = 0.095
μC/cm2).24 Respectively, they are all smaller than that of
-1
Figure 8. Temperature dependence of χMT for 5 (inset: plot of χM
versus T; open circles represent experimental data, and the red line
represents the fit of the data).
complex 4, a rapid loss of one coordinated and three lattice water
molecules was observed with a weight loss of 6.74% (calcd 6.73%)
from 30 °C to 170 °C, and the structure decomposes at 340 °C. The
anhydrous complex 5 begins to decompose at 420 °C. In the case of
complex 6, the network collapses at 390 °C. To confirm whether the
crystal structures are truly representative of the bulk materials,
powder XRD experiments were carried out for compounds 1-6.
The powder XRD experimental and computer-simulated patterns of
the corresponding complexes in Figures S6-S11 in the Supporting
Information show that the bulk synthesized materials and the
measured single crystals are the same.
Photochemical Properties. Luminescent compounds are of
great interest for their various applications in chemical sensors
and photochemistry. The luminescent properties of free ligands
BIDPE, 5-OH-H2bdc, and complexes 1 and 3 in the solid state at
room temperature are investigated, as depicted in Figure S1 in
the Supporting Information. Medium emissions of the free
5-OH-H2bdc and BIDPE ligands were observed at wavelengths
of 350-410 nm (λmax = 362 and 395 nm), which could be
attributed to the π* f π or π* f n transitions. Complexes 1 and
3 exhibit mission characteristics similar to the free ligands. The
emission peaks at 417 nm (λex = 365 nm) in 1 and 415 nm (λex =
362 nm) in 3 show a small red shift, compared to that of the
5-OH-H2bdc and BIDPE ligands, which is probably due to the
intraligand transition of the coordinated ligands. The enhance-
ment of luminescence of complex 3 is mainly attributed to the
polycatenated architecture, which causes a compact stack of
typical ferroelectric compound (e.g., NaKC4H4O6 4H2O
3
(Rochelle salt), which usually has a saturation polarization of
Ps = 0.25 μC/cm2).
Magnetic Properties of Complex 5. The magnetic mea-
surements were performed on polycrystalline samples of 5,
using a SQUID magnetometer under an applied field of 2000
Oe over a temperature range of 2-300 K. The temperature
dependence of the magnetic susceptibility of 5 in the forms of
χMT and χM versus T is displayed in Figure 5. At room
temperature, the value of product χMT is 8.73 cm3 K mol-1
,
which agrees well with the expected value of 8.75 cm3 K mol-1
for two isolated high-spin Mn(II) ions (g = 2 and S = 5/2). Upon
cooling, the χMT value decreases continuously, reaching a value
of 0.62 cm3 K mol-1 at 2 K, suggesting antiferromagnetic
coupling.
The magnetic susceptibility data in the temperature range of
17-300 K can be well-fitted to the Curie-Weiss law with C =
9.02 cm3 mol-1 K and θ = -11.57 K, which further confirms an
overall antiferromagnetic interaction between the MnII ions
(Figure 8). Although this is observed at very low temperatures,
where some anisotropy may be significant, Mn(II) is expected to
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be Heisenberg-like in its magnetic behavior.25 The best fit of the
magnetic data above 2 K in terms of the Heisenberg 1-D chain,
using eqs 1 and 2, and intrachain coupling J gives the following
parameters: J = 0.62 cm-1, zj0 = -0.92 cm-1, and g = 2.02. These
results indicate that there exists very weak antiferromagentic
interaction within the Mn2 unit.26
’ REFERENCES
(1) (a) Leininger, S.; Olenyuk, B.; Stang, P. J. Chem. Rev. 2000, 100,
853. (b) Rajput, L.; Vladimir, V.; Chernyshev; Biradha, K. Chem.
Commun. 2010, 35, 6530. (c) Ma, Y.; Cheng, A. L.; Gao, E. Q. Cryst.
Growth Des. 2010, 7, 2832. (d) Zou, R. Q.; Zhong, R. Q.; Du, M.;
Kiyobayashia, T.; Xu, Q. Chem. Commun. 2007, 2467.
(2) (a) Pang, J.; Marcotte, E. J. P.; Seward, C.; Brown, R. S.; Wang, S.
Angew. Chem., Int. Ed. 2001, 40, 4042. (b) Liang, K.; Zheng, H. G.; Song,
Y. L.; Lappert, M. F.; Li, Y. Z.; Xin, X. Q.; Huang, Z. X.; Chen, J. T.; Lu,
S. F. Angew. Chem., Int. Ed. 2004, 43, 5776. (c) Huang, Y. Q.; Ding, B.;
Song, H. B.; Zhao, B.; Ren, P.; Cheng, P.; Wang, H. G.; Liao, D. Z.; Yan,
S. P. Chem. Commun. 2006, 4906. (d) Bauer, C. A.; Timofeeva, T. V.;
Settersten, T. B.; Patterson, B. D.; Liu, V. H.; Simmons, B. A.; Allendorf,
M. D. J. Am. Chem. Soc. 2007, 129, 7136. (e) Zheng, X. L.; Liu, Y.; Pan,
M.; L€u, X. Q.; Zhang, J. Y.; Zhao, C. Y.; Tong, Y. X.; Su, C. Y. Angew.
Chem., Int. Ed. 2007, 46, 7399. (f) Allendorf, M. D.; Bauer, C. A.;
Bhaktaa, R. K.; Houka, R. J. T. Chem. Soc. Rev. 2009, 38, 1330. (g) Feng,
R. F.; Jiang, L.; Chen, L.; Yan, C. F.; Wu, M. Y.; Hong, M. C. Chem.
Commun. 2009, 5296.
2Ng2β2
χM
¼
kT
55e30J=ðkTÞ þ 30e20J=ðkTÞ þ 14e12J=ðkTÞ þ 5e6J=ðkTÞ þ e2J=ðkTÞ
11e30J=ðkTÞ þ 9e20J=ðkTÞ þ 7e12J=ðkTÞ þ 5e6J=ðkTÞ þ 3e2J=ðkTÞ þ 1
ð1Þ
ꢀ
χ
χM
¼
ð2Þ
1 - ½2zj0=ðNg2β2Þꢁχ
(3) (a) Brechin, E. K.; Harris, S. G.; Harrison, A.; Parsons, S.;
Whittaker, A. G.; Winpenny, R. E. P. Chem. Commun. 1997, 653. (b)
Lu, J. Y.; Lawandy, M. A.; Li, J. Inorg. Chem. 1999, 38, 2695. (c) Kumagai,
H.; Kepert, C. J.; Kurmoo, M. Inorg. Chem. 2002, 41, 3410. (d) Cao, R.;
Shi, Q.; Sun, D. F.; Hong, M. C.; Bi, W. H.; Zhao, Y. J. Inorg. Chem. 2002,
41, 6161. (e) Gavrilenko, K. S.; Punin, S. V.; Cador, O.; Golhen, S.;
Ouahab, L.; Pavlishchuk, V. V. J. Am. Chem. Soc. 2005, 127, 12246. (f)
Pan, Z. R.; Zheng, H. G.; Wang, T. W.; Song, Y.; Li, Y. Z.; Guo, Z. J.;
Batten, S. R. Inorg. Chem. 2008, 47, 9528. (g) Bi, Y. F.; Wang, X. T.;
Wang, B. W.; Liao, W. P.; Wang, X. F.; Zhang, H. J.; Gao, S.; Lia, D. Q.
Dalton Trans. 2009, 2250.
(4) (a) Wu, C. D.; Hu, A. G.; Zhang, L.; Lin, W. B. J. Am. Chem. Soc.
2005, 127, 8940. (b) Alaerts, L.; Seguin, E.; Poelman, H.; Starzyk, F. T.;
Jacobs, P. A.; Vos, D. E. D. Chem.-Eur. J. 2006, 12, 7353. (c) Cho, S. H.;
Ma, B.; Nguyen, S. T.; Hupp, J. T.; Albrecht-Schmitt, T. E. Chem. Commun.
2006, 2563. (d) Xamena, F. X. L.; Abad, A.; Corma, A.; Garcia, H. J. Catal.
2007, 250, 294. (e) Liao, Z. L.; Li, G. D.; Bi, M. H.; Chen, J. S. Inorg. Chem.
2008, 47, 4844. (f) Wu, J.; Hou, H. W.; Guo, Y. X.; Fan, Y. T.; Wang, X. Eur.
J. Inorg. Chem. 2009, 19, 2796. (g) Corma, A.; García, H.; Llabrꢀes i Xamena,
F. X. Chem. Rev. 2010, 110, 4606. (h) Malla Reddy, C.; Rama Krishna, G.;
Soumyajit, G. CrystEngComm 2010, 12, 2296.
(5) (a) Fꢀerey, G.; Latroche, M.; Serre, C.; Millange, F.; Loiseau, T.;
Guꢀegan, A. P. Chem. Commun. 2003, 2976. (b) Rowsell, J. L. C.;
Millward, A. R.; Park, K. S.; Yaghi, O. M. J. Am. Chem. Soc. 2004, 126,
5666. (c) Maji, T. K.; Mostafa, G.; Chang, H. C.; Kitagawa, S. Chem.
Commun. 2005, 2436. (d) Wong-Foy, A. G.; Matzger, A. J.; Yaghi, O. M.
J. Am. Chem. Soc. 2006, 128, 3494. (e) Lin, X.; Jia, J.; Zhao, X.; Thomas,
K. M.; Blake, A. J.; Walker, G. S.; Champness, N. R.; Hubberstey, P.;
Schr€oder, M. Angew. Chem., Int. Ed. 2006, 45, 7358. (f) Liu, Y. L.;
Eubank, J. F.; Cairns, A. J.; Eckert, J.; Kravtsov, V. C.; Luebke, R.;
Eddaoudi, M. Angew. Chem., Int. Ed. 2007, 46, 3278. (g) Thallapally,
P. K.; Tian, J.; Kishan, M. R.; Fernandez, C. A.; Dalgarno, S. J.; McGrail,
P. B.; Warren, J. E.; Atwood, J. L. J. Am. Chem. Soc. 2008, 130, 16842. (h)
Zhang, Y. B.; Zhang, W. X.; Feng, F. Y.; Zhang, J. P.; Chen, X. M. Angew.
Chem., Int. Ed. 2009, 48, 5287. (i) Ma, L. Q.; Jin, A.; Xie, Z. G.; Lin, W. B.
Angew. Chem., Int. Ed. 2009, 48, 9905. (j) Neofotistou, E.; Malliakas,
C. D.; Trikalitis, P. N. Chem.-Eur. J. 2009, 15, 4523. (k) Lin, J. B.;
Zhang, J. P.; Chen, X. M. J. Am. Chem. Soc. 2010, 132, 6654.
(6) (a) Cui, Y.; Evans, O. R.; Ngo, H. L.; White, P. S.; Lin, W. B.
Angew. Chem., Int. Ed. 2002, 41, 1159. (b) Yaghi, O. M.; O’Keeffe, M.;
Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Nature 2003, 423,
705. (c) Carballoa, R.; Coveloa, B.; Lꢀopeza, E. M. V.; Martíneza, E. G.;
Casti~neirasb, A.; Niclꢀosc, J. Z. Anorg. Allg. Chem. 2005, 631, 785. (d)
Reger, D. L.; Watson, R. P.; Smith, M. D. Inorg. Chem. 2006, 45, 10077.
(e) Luo, F.; Che, Y. X.; Zheng, J. M. Cryst. Growth Des. 2009, 9, 1066.
(7) (a) Dybtsev, D. N.; Chun, H.; Kim, K. Chem. Commun. 2004,
1594. (b) Dong, Y. B.; Xu, H. X.; Ma, J. P.; Huang, R. Q. Inorg. Chem.
2006, 45, 3325. (c) Tian, Y. Q.; Zhao, Y. M.; Chen, Z. X.; Zhang, G. N.;
’ CONCLUSION
In summary, six new complexes (identified as 1-6) have been
synthesized via the self-assembly of BIDPE, 5-OH-H2bdc, and
H3btc ligands under solvothermal conditions. It was found that
the BIDPE can change the angles to meet the requirements of
coordination, and the carboxylic groups display a rich coordi-
nated fashion. Complexes 1 and 2 have similar 2D frameworks. In
the case of 3, the noted feature is described as six identical 2D
sheets that polycatenate to form a 2D f 2D framework. Com-
plex 4 is an infinitely double-stranded 1D chain, which further
generates a 3D framework via hydrogen-bonded interactions.
Complex 5 contains binuclear Mn clusters. Complex 6 is a 2-fold
interlocked 2D sheet with strong hydrogen bondings. The results
demonstrate that the noncoordinated carboxyl groups of 5-OH-
H2bdc and H3btc can be well-used as the structure-directing tool
and can produce various hydrogen bonding in the synthesis of
unusual coordination frameworks. In addition, ferroelectric, mag-
netic, and photochemical properties have been studied. These
properties reveal that they are potential multifunctional materials.
Subsequent works will be focused onthe structures andproperties
of a series of coordination complexes constructed by BIDPE with
more auxiliary ligands and metal ions.
’ ASSOCIATED CONTENT
S
Supporting Information. Crystallographic data in CIF
b
format, selected bond lengths and angles, and patterns of
photochemistry, TGA, and powder XRD. This information is
available free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mails: zhenghg@nju.edu.cn (H. Z.), xue@ion.chem.utk.edu
(Z. X.). Fax: 86-25-83314502.
’ ACKNOWLEDGMENT
This work was supported by grants from the Natural Science
Foundation of China (Nos. 91022011, 20971065, 21021062),
National Basic Research Program of China (2007CB925103,
2010CB923303), and U.S. National Science Foundation (CHE-
1012173 to Z.X.).
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Weng, L. H.; Zhao, D. Y. Chem.-Eur. J. 2007, 13, 4146. (d) Sarma, R.;
Kalita, D.; Baruah, J. B. Dalton Trans. 2009, 7428.
(15) Van Der Sluis, P.; Spek, A. L. Acta Crystallogr., Sect. A: Found
Crystallogr. 1990, 46, 194.
(16) Dai, J. C.; Wu, X. T.; Fu, Z. Y.; Cui, C. P.; Hu, S. M.; Du, W. X.;
Wu, L. M.; Zhang, H. H.; Sun, R. Q. Inorg. Chem. 2002, 41, 1391.
(17) (a) Ma, L. F.; Wang, Y. Y.; Liu, J. Q.; Yang, G. P.; Du, M.; Wang,
L. Y. CrystEngComm 2009, 11, 1800. (b) Thomas, A. Z.; Helmar, G.;
Eckhard, D. Polyhedron 1998, 17, 2199.
(18) Carlucci, L.; Ciani, G.; Proserpio, D. M. Coord. Chem. Rev.
2003, 246, 247.
(19) Dong, Z.; Wang, Y. Yu.; Liu, R. T.; Liu, J. Q.; Cui, L.; Shi, Q. Z.
Cryst. Growth Des. 2010, 8, 3311.
(8) (a) Cao, R.; Sun, D. F.; Liang, Y. C.; Hong, M. C.; Tatsumi, K.;
Shi, Q. Inorg. Chem. 2002, 41, 2087. (b) MacDonald, J. C.; Luo,
T. J. M.; Palmore, G. T. R. Cryst. Growth Des. 2004, 4, 1203. (c)
Mahata, P.; Natarajan, S. Inorg. Chem. 2007, 46, 1250. (d) Wang,
Z. W.; Ji, C. C.; Li, J.; Guo, Z. J.; Li, Y. Z.; Zheng, H. G. Cryst. Growth
Des. 2009, 9, 475.
(9) (a) Masaoka, S.; Tanaka, D.; Nakanishi, Y.; Kitagawa, S. Angew.
Chem., Int. Ed. 2004, 43, 2530. (b) Sun, D. F.; Ke, Y. X.; Mattox, T. M.;
Ooro, B. A.; Zhou, H. C. Chem. Commun. 2005, 5447. (c) Zheng, B.;
Dong, H.; Bai, J. F.; Li, Y. Z.; Li, S. H.; Scheer, M. J. Am. Chem. Soc. 2008,
130, 7778. (d) Kanoo, P.; Gurunatha, K. L.; Maji, T. K. Cryst. Growth
Des. 2009, 9, 4147.
(10) (a) Qi, Y.; Che, Y. X.; Zheng, J. M. CrystEngComm 2008, 10,
1137. (b) Henninger, S. K.; Habib, H. A.; Janiak, C. J. Am. Chem. Soc.
2009, 131, 2776. (c) Ma, L. F.; Wang, L. Y.; Wang, Y. Y.; Du, Miao;
Wang, J. G. CrystEngComm 2009, 11, 109. (d) Habib, H. A.; Sanchiz, J.;
Janiak, C. Inorg. Chim. Acta 2009, 362, 2452. (e) Habib, H. A.;
Hoffmann, A.; Hoppe, H. A.; Janiak, C. Dalton Trans. 2009, 1742. (f)
Habib, H. A.; Sanchiz, J.; Janiak, C. Dalton Trans. 2008, 1734. (g) Zhang,
L. P.; Yang, J.; Ma, J. F.; Jia, Z. F.; Xie, Y. P.; Wei, G. H. CrystEngComm
2008, 10, 1410. (h) Wisser, B.; Lu, Y.; Janiak, C. Z. Anorg. Allg. Chem.
2007, 633, 1189. (i) Manna, S. C.; Okamoto, K. I.; Zangrando, E.;
Chaudhuri, N. R. CrystEngComm 2007, 9, 199. (j) Chen, Z. F.; Zhang,
S. F.; Luo, H. S.; Abrahams, B. F.; Liang, H. CrystEngComm 2007, 9, 27.
(k) Pichon, A.; Fierro, C. M.; Nieuwenhuyzen, M.; James, S. CrystEng-
Comm 2007, 9, 449. (l) Pasan, J.; Sanchiz, J.; Lloret, F.; Julve, M.; Ruiz-
Perez, C. CrystEngComm 2007, 9, 478. (m) Stephenson, M. D.; Hardie,
M. J. Dalton Trans. 2006, 3407. (n) Carballo, R.; Covelo, B.; Vazquez-
Lopez, E. M.; García-Martínez, E.; Casti~neiras, A.; Janiak, C. Z. Anorg.
Allg. Chem. 2005, 631, 2006. (o) Yao, J.; Lu, Z. D.; Li, Y. Z.; Lin, J. G.;
Duan, X. Y.; Gao, S.; Meng, Q. J.; Lu, C. S. CrystEngComm 2008, 10,
1379. (p) Wei, G. H.; Yang, J.; Ma, J. F.; Liu, Y. Y.; Li, S. L.; Zhang, L. P.
Dalton Trans. 2008, 3080. (q) Zhang, J. Y.; Ma, Y.; Cheng, A. L.; Yue, Q.;
Sun, Q.; Gao, E. Q. Dalton Trans. 2008, 2061.
(20) Yi, L.; Zhu, L. N.; Ding, B.; Cheng, P.; Liao, D. Z.; Yan, S. P.;
Jiang, Z. H. Inorg. Chem. Commun. 2003, 6, 1209.
(21) (a) Wang, B. C.; Wu, Q. R.; Hu, H. M.; Chen, X. L.; Yang, Z. H.;
Shangguan, Y. Q.; Yang, M. L.; Xue, G. L. CrystEngComm 2010, 12, 485.
(b) Jeremiꢀc, D. J.; Kaluderoviꢀc, G. N.; Gꢀomez-Ruiz, S.; Brꢁceski, I.;
Kasalica, B.; Leovac, V. M. Cryst. Growth Des. 2010, 10, 559.
(22) Li, X.; Sun, H. L.; Wu, X. S.; Qiu, X.; Du, M. Inorg. Chem. 2010,
49, 1865.
(23) (a) Zhao, H.; Qu, Z. R.; Ye, Q.; Abrahams, B. F.; Wang, Y. P.;
Liu, Z. G.; Xue, Z. L.; Xiong, R. G.; You, X. Z. Chem. Mater. 2003, 15,
4166. (b) Okubo, T.; Kawajiri, R.; Mitani, T.; Shimoda, T. J. Am. Chem.
Soc. 2005, 127, 17598. (c) Ohkoshi, S. I.; Tokoro, H.; Matsuda, T.;
Takahashi, H.; Irie, H.; Hashimoto, K. Angew. Chem., Int. Ed. 2007, 46,
3238. (d) Zhou, W. W.; Chen, J. T.; Xu, G.; Wang, M. S.; Zou, J. P.;
Long, X. F.; Wang, G. J.; Guo, G. C.; Huang, J. S. Chem. Commun. 2008,
2762. (e) Nakagawa, K.; Tokoro, H.; Ohkoshi, S. Inorg. Chem. 2008, 47,
10810. (f) Wang, C. F.; Li, D. P.; Chen, X.; Li, X. M.; Li, Y. Z.; Zuo, J. L.;
You, X. Z. Chem. Commun. 2009, 6940. (g) Zhao, H. R.; Li, D. P.; Ren,
X. M.; Song, Y.; Jin, W. Q. J. Am. Chem. Soc. 2010, 132, 18.
(24) Liang, X. Q.; Li, D. P.; Li, C. H.; Zhou, X. H.; Li, Y. Z.; Zuo, J. L.;
You., X. Z. Cryst. Growth Des. 2010, 6, 2596.
(25) Kennedy, B. J.; Murray, K. S. Inorg. Chem. 1985, 24, 1552.
(26) (a) Chen, Z. L.; Jiang, C. F.; Yan, W. H.; Liang, F. P.; Batten,
S. R. Inorg. Chem. 2009, 48, 4674. (b) Pan, Z. R.; Song, Y.; Jiao, Y.; Fang,
Z. J.; Li, Y. Z.; Zheng, H. G. Inorg. Chem. 2008, 47, 5162.
(11) (b) Zaworotko, M. J. Chem. Commun. 2000, 1. (a) Barnett,
S. A.; Champness, N. R. Coord. Chem. Rev. 2003, 246, 145. (c) Roesky,
H. W.; Andruh, M. Coord. Chem. Rev. 2003, 236, 91.
(12) (a) Hoskins, B. F.; Robson, R.; Slizys, D. A. Angew. Chem., Int.
Ed. 1997, 36, 2752. (b) Liu, H. K.; Sun, W. Y.; Ma, D. J.; Yu, K. B.; Tang,
W. X. Chem. Commun. 2000, 591. (c) Ma, J. F.; Yang, J.; Zheng, G. L.; Li,
L.; Liu, J. F. Inorg. Chem. 2003, 42, 7531. (d) Zhao, W.; Fan, J.; Okamura,
T.; Sun, W.-Y.; Ueyama, N. New J. Chem. 2004, 28, 1142. (e) Fan, J.;
Hanson, B. E. Inorg. Chem. 2005, 44, 6998. (f) Cui, G. H.; Li, J. R.; Tian,
J. L.; Bu, X. H.; Batten, S. R. Cryst. Growth Des. 2005, 5, 1775. (g) Wen,
L. L.; Dang, D. B.; Duan, C. Y.; Li, Y. Z.; Tian, Z. F.; Meng, Q. J. Inorg.
Chem. 2005, 44, 7161. (h) Yang, J.; Ma, J. F.; Liu, Y. Y.; Ma, J. C.; Batten,
S. R. Cryst. Growth Des. 2008, 8, 4383. (i) Qi, Y.; Luo, F.; Che, Y. X.;
Zheng, J. M. Cryst. Growth Des. 2008, 8, 606. (j) Li, F. F.; Ma, J. F.; Song,
S. Y.; Yang, J.; Jia, H. Q.; Hu, N. H. Cryst. Growth Des. 2006, 6, 209. (k)
Goodgame, D. M. L.; Menzer, S.; Williams, D. J. Chem. Commun 1996,
2127. (l) Hoskins, B. F.; Robson, R.; Slizys, D. A. J. Am. Chem. Soc. 1997,
119, 2952. (m) Carlucci, L.; Ciani, G.; Proserpio, D. M. Chem. Commun.
2004, 380. (n) Wen, L. L.; Dang, D. B.; Duan, C. Y.; Li, Y. Z.; Tian, Z. F.;
Meng, Q. J. Inorg. Chem. 2005, 44, 7161. (o) Zhu, H. F.; Fan, J.;
Okamura, T.-a.; Sun, W. Y.; Ueyama, N. Cryst. Growth Des. 2005, 5, 289.
(p) Lin, J.-D.; Li, Z.-H.; Li, J.-R.; Du, S.-W. Polyhedron 2007, 26 (1), 107.
(q) Song, L.; Li, J. R.; Lin, P.; Li, Z. H.; Li, T.; Du, S. W.; Wu, X. T. Inorg.
Chem. 2006, 45, 10155. (r) Tian, Z. F.; Lin, J. G.; Su, Y.; Wen, L. L.; Liu,
Y. M.; Zhu, H. Z.; Meng, Q. J. Cryst. Growth Des. 2007, 7, 1863. (s)
Carlucci, L.; Ciani, G.; Maggini, S.; Proserpio, D. M. Cryst. Growth Des.
2008, 8, 162.
(13) Hu, J. S.; Shang, Y. J.; Yao, X. Q.; Qin, L.; Li, Y. Z.; Guo, Z. J.;
Zheng, H. G.; Xue, Z. L. Cryst. Growth Des. 2010, 10, 4135.
(14) Bruker 2000, SMART (Version 5.0), SAINT-plus (Version 6),
SHELXTL (Version 6.1), and SADABS (Version 2.03); Bruker AXS, Inc.:
Madison, WI.
2414
dx.doi.org/10.1021/ic102207n |Inorg. Chem. 2011, 50, 2404–2414