Structural transformation mediated by o-, m-, and p-phthalates from two to three dimensions for manganese/phthalate/4,4′-bpy complexes (4,4′-bpy = 4,4′-bipyridine)

Article abstract of DOI:10.1039/b301076g

Three isomers of o-, m-, and p-phthalate are used to link together Mn centres, resulting in [Mn(phth)(H₂O)_x]_n moieties (phth = phthalate dianion) with single-chain, double-chain and sheet structures, respectively, which pr

Full text of DOI:10.1039/b301076g

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Structural transformation mediated by o-, m-, and p-phthalates from
two to three dimensions for manganese/phthalate/4,40-bpy complexes
(4,40-bpy ¼ 4,40-bipyridine)
Chengbing Ma,ad Changneng Chen,a Qiutian Liu,*a Daizheng Liao,b Licun Lib and Licheng Sunc
a
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure
of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
E-mail: lqt@ms.fjirsm.ac.cn
Department of Chemistry, Nankai University, Tainjin 300071, China
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, China
Graduate School of the Chinese Academy of Sciences, Beijing, China
b
c
d
Received (in London, UK) 27th January 2003, Accepted 13th March 2003
First published as an Advance Article on the web 11th April 2003
Three isomers of o-, m-, and p-phthalate are used to link together Mn centres, resulting in [Mn(phth)(H2O)x]n
moieties (phth ¼ phthalate dianion) with single-chain, double-chain and sheet structures, respectively, which
predetermine the extended structures derived from the crosslinkage of 4,40-bipyridine, and show the influence
of isomerism of the phthalate on topological changes of the final polymers from two dimensional (2D)
single-layer, double-layer to 3D network architectures. These structural changes in topology are correlated
with the differences in the magnetic and optical properties of the polymers.
L1 completes the coordination equatorial plane, forming 1D
Introduction
chain or 2D layer structures, while exo-bidentate axial ligand
L2 as a secondary spacer leads to the final architectures with
higher dimensionality. Three manganese(II) polymers are
reported in this work, exhibiting systematic structural varia-
tion from 2D single-layer to 2D double-layer to 3D network.
Their magnetic behaviors and fluorescence are also presented.
Pronounced attention has currently been paid to the crystal
engineering of 2D and 3D metal–ligand coordination polymers
due to their fascinating network topologies and potential
applications as functional materials.1,2 Despite the upsurge in
the construction of diverse architectures, the control of dimen-
sionality is still a major challenge in this field3 due to the fact
that the resultant structural framework is frequently influenced
by various factors such as medium, temperature, metal–ligand
ratio, template and counter-ion.4 In a spontaneous assembly
process, the structural information stored in the organic ligand
is read by the metal ion through its coordination geometry
from the programmed system.5 By the judicious choice of the
organic spacer and the central metal, it is possible to elaborate
a specific architecture, and even to create expected properties
related to the architecture. Scheme 1 illustrates the controlled
formation of the topological framework, which predictably
varies from 2D (single-layer, double-layer, etc.) to 3D for
the given octahedral metal. In this process, primary ligand
Synthesis
We have reported a double-chain structure of a Mn complex
6
[Mn(m-phth)(C5H5N)2]n with m-phthalate as the primary
ligand L1 for the first time by using monodentate pyridine as
the secondary axial ligand (L2) as shown in Scheme 2. It seems
to be predictable that exo-bidentate 4,40-bipyridine (4,40-bpy)
should lead to the 2D double-layer structure if it is used as
L2 instead of monodentate pyridine. Three phthalate isomers
are picked out as the primary ligand, in view of their versatile
bonding modes with metal ion(s), together with 4,40-bpy as the
Scheme 1 Schematic representation of assembly for possible architectures. Octahedral metal (black ellipse) is coordinated by primary ligands L1
in the equatorial plane to form single-chain (N ¼ 1), double-chain (N ¼ 2) and sheet motifs (N ¼ n). Secondary organic spacers L2 enter axial
positions, forming 2D single-layer, 2D double-layer, and 3D network structures. The capital letter N stands for the number of layers in the [MnL1]n
motif.
890
New J. Chem., 2003, 27, 890–894
DOI: 10.1039/b301076g
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Scheme 2 A double chain structure of [Mn(m-phth)(py)2]n .
secondary spacer, to observe the influence of isomerism of the
phthalate on the topology of the synthesized Mn polymers.
Hydrothermal reactions of MnCO3 with o, m, or p-phthalic
acid isomers and 4,40-bpy were performed in water–ethanol
at 160 ꢀC, affording [Mn(o-phth)(4,40-bpy)(H2O)2]n (1),
[Mn(m-phth)(4,40-bpy)]n (2) and [Mn(p-phth)(4,40-bpy)]n (3),
respectively, in moderate yields.
Structure and dimensionality
The three compounds are constructed from [Mn(phth)
(H2O)x]n (L ¼ o-phth, x ¼ 2 and L ¼ m- or p-phth, x ¼ 0)
motifs linking 4,40-bpy spacers. The motif of 1 has a single-
chain structure (Fig. 1a), in which two carboxyls of the o-phth
ligand coordinate monodentately to two Mn centers forming a
Mn–phth–Mn linkage and two water molecules are located at
opposite sides of the equatorial plane. This motif is different
from that found in [Mn(o-phth)(phen)(H2O)2]nꢁH2O,7 in which
o-phth employs one carboxyl bridging Mn atoms to form a
chain structure with another carboxyl free. [Mn(m-phth)]n con-
tains a parallel double-chain with respect to the Mn atoms, in
which the one carboxyl of the m-phth chelates to a Mn and the
other bridges between two Mn atoms (Fig. 1b). A quite differ-
ent example was found to be [Zn4(m-phth)4(m4-O)(bpy)4]n ,8 in
which the Zn4O cores are bridged by bis-monodentate and bis-
bidentate m-phth ligands into 1D ladder-like [Zn4O(m-phth)3]
chains. [Mn(p-phth)]n has a parallelogram-grid sheet structure.
Every p-phth ligand in m4-bridging mode links two pairs of
adjacent Mn atoms, resulting in 1D linear chains with
Fig. 2 Perspective views of the frameworks pillared by 4,40-bpy for
three manganese polymers: (a) 2D single-layer, (b) 2D double-layer,
and (c) 3D network in 1, 2 and 3, respectively.
The three motifs mentioned above are further linked by
bidentate 4,40-bpy along the axial positions of the Mn octahe-
dron, creating three different architectures: a 2D wavy single-
layer of 1 having rectangular grids with dimensions of
˚
7.704(1) ꢂ 11.586(1) A (Fig. 2a), a 2D parallel double-layer
˚
of 2 with an interlayer separation of ca. 2.625(5) A (Fig. 2b)
˚
Mnꢁ ꢁ ꢁMn separation of 4.196(2) A, which are further inter-
and a 3D two-fold interpenetrating network of 3 contain-
˚
linked through p-phth ligands in bis-bidentate chelating mode
to fabricate a 2D sheet (Fig. 1c). A similar coordination mode
of p-phth to that in 3 has been found in [Co(p-phth)(bpy)]n .9
ing 1D channels with dimensions of 11.598(1) ꢂ 10.929(1) A
(Fig. 2c). Selected bond distances and angles are listed in
Table 1. Unlike 1 and 2, no guest molecules are encapsulated
in 3 due to the large pores which are actually filled by interpe-
netration of a second network. The complicated coordination
modes of o- and p-phth ligands in 1 and 3 are rarely found,
though similar structures to 1 and 3 have occurred in three
Co and Cd complexes.9,10 As mentioned previously, the dou-
ble-chain motif of the m-phth ligand has recently been
reported,6 which leads to complex 2 with a novel double-layer
structure pillared by 4,40-bpy. A few metal complexes with
bilayer11 or trilayer12 structures have been reported.
A notable structural feature in the three polymers is the
occurrence of [Mn(phth)(H2O)x]n subunits, which predeter-
mine the extended orientations of the final structure. It is logi-
cal that the smallest separation of carboxyls in o-phth
compared to that in m- and p-isomers results in crowding of
the groups, which is favorable for the monodentate coordina-
tion of both the o-COO groups to Mn ions, forming a [Mn-
(o-phth)(H2O)2]n single-chain structure. It is also noted that,
with the decrease of the steric crowding of the two carboxylic
groups, the dihedral angle between them becomes smaller from
54.4(5)ꢀ in 1 to 12.8(5)ꢀ in 2. A similar variation of the dihedral
angle between the carboxylic group and the neighbouring ben-
zene ring is also observed from 120.6(1)ꢀ in 1 to 11.3(2)ꢀ in 2.
In complex 3, all the carboxyl groups in the same layer are
strictly coplanar, and the coplanarity can extend to include
all the Mn sites and the m4-p-phth ligands. Obviously, it is
the isomeric phthalates that play a vital role in the controlled
Fig. 1 Structures of three motifs in 1, 2 and 3. (a) 1D single-chain of
Mn(o-phth)(H2O)2 , (b) 1D double-chain of Mn(m-phth), and (c) 2D
sheet of Mn(p-phth). Selected atoms are labeled with the Mn chains
dotted and 4,40-bpy omitted. Possible magnetic interaction routes are
indicated.
New J. Chem., 2003, 27, 890–894
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ꢀ
˚
Table 1 Selected bond distances (A) and angles ( ) of 1, 2 and 3
the phthalate ligand and a short m-OCO way (J2). Eqns. 1
and 2 were used to fit the magnetic data of 1 and 2, respec-
tively.
1
ꢀ
ꢁ
Mn–O1
Mn–N1
2.196(2)
2.252(4)
Mn–O3
Mn–N2B
2.203(2)
2.268(4)
92.91(9)
178.45(12)
90.77(6)
89.23(6)
Ng2m2B
kT
w1 ¼
½A þ Bx2ꢃ½1 þ Cx þ Dx3ꢃꢄ1
O1–Mn–O1A
O1–Mn–O3
O1–Mn–N1
O1–Mn–N2B
N1–Mn–N2B
2
172.73(12)
86.99(8)
93.64(6)
O1–Mn–O3A
O3–Mn–O3A
O3–Mn–N1
O3–Mn–N2B
A ¼ 2:9167; B ¼ 208:04; C ¼ 15:543;
D ¼ 2707:2; x ¼ j Jl j=kT
ð1Þ
86.36(6)
180.00(1)
ꢀ
ꢁ
Ng02 mB2 1 þ u1 þ u2 þ u1u2
w2 ¼
Mn–O1
Mn–O4A
Mn–N1
2.142(3)
2.227(3)
2.266(3)
Mn–O2B
Mn–N2C
Mn–O3A
2.101(3)
2.232(4)
2.302(3)
3kT
1 ꢄ u1u2
ꢀ
ꢁ
ꢀ
ꢁ
J0
kT
J0
J0
kT
J0
1
2
u1 ¼ Coth
ꢄ
u2 ¼ Coth
ꢄ
O2B–Mn–O1
O1–Mn–O4A
O1–Mn–N2C
O2B–Mn–N1
O4A–Mn–N1
O2B–Mn–O3A
O4A–Mn–O3A
N1–Mn–O3A
3
124.22(11)
145.46(11)
90.68(11)
88.20(12)
91.12(12)
147.43(11)
57.25(10)
90.02(13)
O2B–Mn–O4A
O2B–Mn–N2C
O4A–Mn–N2C
O1–Mn–N1
N2C–Mn–N1
O1–Mn–O3A
N2C–Mn–O3A
90.26(12)
88.43(12)
92.35(12)
88.36(11)
175.17(12)
88.22(10)
94.68(13)
kT
kT
1
2
1=2
J0 ¼ JiSðS þ 1Þ ði ¼ 1; 2Þ; g0 ¼ g½SðS þ 1Þꢃ
ð2Þ
i
The best fitting parameters were found to be J1 ¼ ꢄ0.01
cmꢄ1
,
g ¼ 2.01, and R ¼ 3.89 ꢂ 10ꢄ4 for 1, J1 ¼ ꢄ0.08
cmꢄ1, J2 ¼ ꢄ1.05 cmꢄ1, g ¼ 2.01, and R ¼ 5.57 ꢂ 10ꢄ5 for 2.
For 3, it was first treated as a dinuclear manganese unit
Mn2(m-OCO)2 with the interaction being J1 .
Mn–O4A
Mn–O2
Mn–N1
2.065(3)
2.193(3)
2.278(4)
Mn–O3
Mn–N2B
Mn–O1
2.106(3)
2.266(4)
2.356(3)
^
^
^
H ¼ ꢄJ1S1 ꢁS2
ð2Þ
These dinuclear units can be seen as entities with effective
classical spin Sbi which link each other through planar m4-p-
phth bridges to form a 1D chain with the magnetic exchange
constant (J2) between the Mn ions of neighboring entities. This
1D Sbi chain can be treated according to eqn. 3 to obtain the
susceptibility values.
O4A–Mn–O3
O3–Mn–O2
O3–Mn–N2B
O4A–Mn–N1
O2–Mn–N1
O4A–Mn–O1
O2–Mn–O1
N1–Mn–O1
116.31(13)
91.57(12)
94.22(13)
88.18(13)
83.94(14)
95.09(12)
57.07(11)
89.28(14)
O4A–Mn–O2
O4A–Mn–N2B
O2–Mn–N2
O3–Mn–N1
N2B–Mn–N1
O3–Mn–O1
N2B–Mn–O1
151.01(13)
90.89(13)
94.97(14)
89.80(13)
175.86(13)
148.54(13)
86.79(13)
ꢀ
ꢁ
Â
Ã
1 þ u
1 ꢄ u
wchain ¼ Ng2b2SbiðSbi þ 1Þ=3kT
ꢂ
ꢃ
J2SbiðSbi þ 1Þ
kT
u ¼ Coth
ꢄ
ð3Þ
kT
J2SbiðSbi þ 1Þ
formation of final architectures with structural systematic
variation by means of specific location and orientation of
two carboxyl groups.
Then a molecular field approximation15 (eqn. 4) was used to
modify the interchain interaction (zJ0) through the chelating p-
phth bridge (Fig. 1c), giving the final susceptibilities of the sys-
tem. The z value is the number of nearest magnetic species
around a given magnetic site in the crystal lattice.
Magnetic properties and emission spectra
wchain
wM
¼
À
Á
ð4Þ
Experimental effective magnetic moments as functions of tem-
perature for 1, 2 and 3 are shown in Fig. 3. Considering a
separation between the Mn(II) centers bridged by 4,40-bpy
which is too long to transfer the magnetic interactions, two
models based on a uniform [Mn(m-o-phth)]n chain13 (Fig. 1a)
and alternating chains14 consisting of Mn2(m-OCO)2 and
Mn2(m3-m-phth)2 moieties (Fig. 1b) were adopted for 1 and
2, respectively. Two possible magnetic exchange interactions
were contained in the models: a long pathway (J1) through
1 ꢄ zJ0=Ng2b2 wchain
The best fitting parameters were found to be J1 ¼ ꢄ0.44
cmꢄ1, J2 ¼ ꢄ0.155 cmꢄ1, zJ0 ¼ ꢄ0.062 cmꢄ1, g ¼ 1.98, and
R ¼ 9.27 ꢂ 10ꢄ4 for 3.
All the magnetic interactions in the three complexes are
weak antiferromagnetic coupling interactions. It is noted that
the magnetic interactions through the short m-OCO pathway
are obviously larger than that through the long pathway
including the benzene ring of the phthlates. The difference in
the magnitude of the magnetic coupling interactions found
for the three complexes can be explained in terms of the brid-
ging modes and the overlap of d–p magnetic orbitals. As
expected on the basis of the respective geometries, an efficient
overlap between the 3d magnetic orbital of the Mn2+ center
and the 2p magnetic orbital of the carboxyl oxygen atom
would lead to antiferromagnetic interactions. As mentioned
previously the three complexes exhibit evidently different
coplanarity between the caboxylic group and neighbouring
benzene ring in the order p- > m- > o- for the isomers. Conse-
quently, the magnitude of the magnetic interactions via the
long pathway becomes 3 > 2 > 1.
The emission spectra in the solid state at room temperature
are shown in Fig. 4 for 1 and 2 and Fig. 5 for 3. There are
significant differences of the emission maxima for the three
complexes. The photoluminescence of 1 exhibits an intense
emission maximum at 610 nm (lexc ¼ 432 nm), while 2 has
complicated spectral features with two stronger emission
Fig. 3 Temperature dependence of effective magnetic moments (meff
for complexes 1, 2 and 3. The solid lines represent the calculated
values.
)
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New J. Chem., 2003, 27, 890–894

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Mn). Anal. Calcd. for C18H20MnN2O8 : C, 48.33; H, 4.51;
N, 6.26; Mn, 12.28. Found: C, 48.37; H, 4.49; N, 6.32;
Mn, 12.33%. IR (KBr pellet, cmꢄ1): n ¼ 3458(s), 3178(br),
1635(m), 1606(s), 1560(s), 1535(w), 1485(m), 1443(m), 1406(s),
1317(w), 1217(w), 1082(w), 1065(w), 1049(w), 1012(m), 947(w),
839(m), 800(w), 764(s), 737(w), 698(w), 671(w), 656(w), 633(s),
567(w), 530(m), 513(w), 444(w).
.
.
2 0.75nH2O 0.25nC2H5OH. The preceding procedure was
utilized with the use of m-phthalic acid instead. Yellow rhom-
bic crystals (0.62 g) were obtained in 77% yield (based on Mn).
Anal. Calcd. for C18.5H15MnN2O5 : C, 55.51; H, 3.78; N, 7.00;
Mn, 13.73. Found: C, 55.55; H, 3.83; N, 6.98; Mn, 13.79%. IR
(KBr pellet, cmꢄ1): n ¼ 3430(br), 3095(w), 3059(m), 2924(w),
2848(w), 1682(s), 1605(s), 1568(s), 1547(s), 1479(m), 1446(s),
1394(s), 1327(w), 1277(w), 1259(w), 1221(m), 1157(w),
1103(m), 1070(s), 1045(s), 1007(s), 960(w), 937(w), 914(m),
881(w), 833(m), 812(s), 741(s), 721(s), 660(m), 629(s), 573(m),
509(w), 428(m).
Fig. 4 Solid state emission spectra of 1 and 2 at room temperature.
3. The preceding procedure was utilized with the use of p-
phthalic acid instead. 0.28 g of light yellow prismatic crystals
were collected in 37% yield (based on Mn). Anal. Calcd. for
C18H12MnN2O4 : C, 57.62; H, 3.22; N, 7.47; Mn, 14.64.
Found: C, 57.58; H, 3.27; N, 7.45; Mn, 14.71%. IR (KBr pellet,
cmꢄ1): n ¼ 3110(w), 1657(m), 1610(s), 1556(s), 1493(w),
1417(s), 1369(s), 1223(m), 1142(w), 1068(s), 1045(w),
1012(m), 891(w), 858(w), 839(w), 812(s), 793(w), 752(s),
729(w), 656(w), 633(s), 573(w), 501(m), 478(m), 442(w).
X-Ray crystallography
Fig. 5 Solid state emission spectrum of 3 at room temperature.
Single crystals of the three complexes were coated with epoxy
resin and mounted on a glass fiber and scanned on a Siemens
Smart CCD diffractometer with Mo Ka radiation (l ¼
maxima at 485 nm and 538 nm, as well as two weaker ones at
419 nm and 712 nm (lexc ¼ 350 nm). 3 exhibits one strong
emission maximum at 420 nm and two weak peaks at 650
nm and 790 nm (lexc ¼ 320 nm). The complicated mixed-
ligand system and the lack of available information on photo-
luminescence for the Mn(II) complex make assignment of the
observed emissions difficult; however, these variations, espe-
cially for the most intense emission, seem to be correlated to
the introduction of three phthalate isomers resulting in corre-
sponding structural variations. Further work is in progress.
In conclusion, we have created three manganese(II) polymers
exhibiting a systematic variation of topologies by the utiliza-
tion of isomeric ligands, and representing a preliminary exam-
ple of realizing structural transformation from single-layer to
double-layer to 3D network. Though approaches of control-
ling the dimensionality of the coordination polymers are devel-
oping, only a few series of isomeric organic ligands, to our
knowledge, have been utilized to study for this purpose. The
isomeric phthalates not only give rise to systematic variation
of structural topologies in the presence of 4,40-bpy for the
given Mn(II) center, but also alter the magnetic and photolumi-
nescent properties, providing crystal engineering with a poten-
tial tool for tuning the crystalline solid architecture and
exploring desirable properties.
˚
0.71073 A) at 293 K using the o–2y scan mode. The structures
were solved by direct methods and refined by full-matrix least
squares on (F2) by using the SHELXTL97 program.16 The metal
ions were first located, while other non-hydrogen atoms were
found in subsequent difference Fourier syntheses. All the
non-hydrogen atoms were refined anisotropically except for
the O8 atom of complex 2, which is in solvate EtOH and has
an occupancy factor of 0.25 in its position which was refined
Table
C2H5OH and 3
2
Crystallographic data for 1ꢁ2nH2O, 2ꢁ0.75nH2Oꢁ0.25n-
2ꢁ0.75nH2Oꢁ0.25
nC2H5OH
Compound
1ꢁ2nH2O
18H20MnN2O8
3
Formula
f.w.
Space group
C
C18.5H15MnN2O5 C18H12MnN2O4
447.30
P2/n
400.26
P2/c
375.24
¯
P1
˚
a/A
7.7038(9)
11.5864(13)
10.7693(12)
90.00
10.116(2)
11.562(2)
16.084(3)
90.00
9.3349(7)
10.3142(8)
11.4065(8)
92.023(1)
112.864(1)
116.479(2)
876.36(11)
2
˚
b/A
˚
c/A
a/ꢀ
b/ꢀ
g/ꢀ
92.691(2)
90.00
102.99(3)
90.00
3
˚
V/A
960.20(19)
2
1.547
1833.0(6)
4
1.450
Z
d
calc/g cmꢄ3
m/mmꢄ1
T/K
1.422
0.777
293
Experimental
0.737
293
0.752
293
Synthesis
ꢀ
2ymax
/
25.02
1694
27.52
3990
25.05
3066
No. unique
reflections
Reflections
.
1 2nH2O. In a typical synthesis, 0.23 g (2 mmol) of MnCO3 ,
0.34 (2 mmol) of o-phthalic acid and 0.31
(Rint ¼ 0.0317)
1292
(Rint ¼ 0.0476)
(Rint ¼ 0.0272)
2313
g
g
2799
(2 mmol) of 4,40-bipyridine and 15 mL of water–ethanol (v/v,
1:1) were sealed in a 25 ml stainless-steel reactor with a teflon
liner. The reactor was heated to 160 ꢀC during 4 hours, and
kept at this temperature for 4 days. This gave 0.48 g of light
yellow block-like crystals of 1ꢁ2H2O in 54% yield (based on
used (I > 2s(I))
a
R1
0.0430
0.1008
0.0631
0.1783
0.0568
0.1379
b
Rw
a
b
R ¼ S||Fo| ꢄ |Fc||/S|Fo|. Rw ¼ [Sw(|Fo| ꢄ |Fc|)2/SwFo2 ]1/2
.
New J. Chem., 2003, 27, 890–894
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3
4
S. S.-Y. Chui, S. M.-F. Lo, J. P. H. Charmant, A. G. Orpen and
I. D. Williams, Science, 1999, 283, 1148–1150.
isotropically. Hydrogen atoms were located by geometric cal-
culation, but their positions and thermal parameters were fixed
during the structure refinement. It is necessary to indicate that
complex 2 contains solvate H2O and EtOH in its lattice, which
were found to form only 0.75 and 0.25 molecules in various
positions. The crystallographic data of the three complexes
are listed in Table 2.
CCDC reference numbers: 190374–190376 for 1–3. See
http://www.rsc.org/suppdata/nj/b3/b301076g/ for crystallo-
graphic data in CIF or other electronic format.
(a) Y. Tokunaga, D. M. Rudkevich and J. Jr. Rebek, Angew.
Chem., Int. Ed. Engl., 1997, 36, 2656–2659; (b) M. A. Withersby,
A. J. Blake, N. R. Champness, P. Hubberstey, W. Li and M.
Schro¨der, Angew. Chem., Int. Ed. Engl., 1997, 36, 2327–2329; (c)
O. M. Yaghi and H. Li, J. Am. Chem. Soc., 1995, 117, 10 401–
10 402; (d ) P. Losier and M. J. Zaworotko, Angew. Chem., Int.
Ed. Engl., 1996, 35, 2779–2781 and references therein; (e)
D. M. J. Dobe, C. H. Benison, A. J. Blake, D. Fenske, M. S.
Jackson, R. D. Kay, W. Li and M. Schro¨der, Angew. Chem., Int.
Ed., 1999, 38, 1915–1918.
5
6
7
8
9
J. M. Lehn, Supramolecular Chemistry-Concepts and Perspectives,
VCH, Weinheim, 1995.
M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. M. Reineke, M. O.
Keeffe and O. M. Yaghi, Acc. Chem. Res., 2001, 34, 319–330.
Y. Zhang, J. Li, M. Zhu, Q. Wang and X. Wu, Chem. Lett., 1998,
1051–1052.
J. Tao, M.-L. Tong, J.-X. Shi, X.-M. Chen and S. W. Ng, Chem.
Commun., 2000, 2043–2044.
J. Tao, M.-L. Tong and X.-M. Chen, J. Chem. Soc., Dalton
Trans., 2000, 3669–3674.
Acknowledgements
This work was supported by NNSFC (No. 30170229), the
State Key Basic Research and Development Plan of China
(G1998010100), and Expert Project of Key Basic Research
from the Ministry of Sci & Tech.
10 E. Suresh, K. Boopalan, R. V. Jasra and M. M. Bhadbhade,
Inorg. Chem., 2001, 40, 4078–4080.
References
11 (a) S. Kitagawa and M. Kondo, Bull. Chem. Soc. Jpn., 1998, 71,
1739–1753; (b) C. J. Kepert and M. J. Rosseinsky, Chem. Com-
mun., 1999, 375–376; (c) A. Rujiwatra, C. J. Kepert and M. J.
Rosseinsky, Chem. Commun., 1999, 2307–2308; (d ) K. N. Power,
T. L. Hennigar and M. J. Zaworotko, New J. Chem., 1998, 22,
177–181; (e) J. Dai, X. Wu, Z. Fu, C. Cui, S. Hui, W. Du,
L. Wu, H. Zhang and R. Sun, Inorg. Chem., 2002, 41, 1391–1396.
12 J. Y. Lu and A. M. Babb, Inorg. Chem., 2001, 40, 3261–3262.
13 W. Hiller, J. Stra¨hle, A. Datz, M. Hanack, W. E. Hatfield, L. W.
1
(a) R. Robson, B. F. Abrahams, S. R. Batten, R. W. Gable,
B. F. Hoskins and J. Liu, Supramolecular Architecture, ACS,
Washington, DC, 1992; (b) S. R. Batten and R. Robson, Angew.
Chem., Int. Ed., 1998, 37, 1460–1494; (c) M. J. Zaworotko, Chem.
Commun., 2001, 1–9; (d ) P. J. Hagrman and J. Zubieta, Angew.
Chem., Int. Ed., 1999, 38, 2638–2384; (e) O. M. Yaghi, H. Li,
C. Davis, D. Richardson and T. L. Groy, Acc. Chem. Res.,
1998, 31, 474–484; ( f ) M. Munakata, L. Wu and T. K. Sowa,
Adv. Inorg. Chem., 1999, 46, 173–197; (g) A. J. Blake, N. R.
Champness, P. Hubberstey, W.-S. Li, M. A. Withersby and M.
Schro¨der, Coord. Chem. Rev., 1999, 183, 117–138; (h) J. M. Lehn,
Angew. Chem., Int. Ed., 1988, 27, 89–112.
(a) O. Kahn and C. Martinez, Science, 1998, 279, 44–48; (b) O. M.
Yaghi, G. M. Li and H. L. Li, Nature, 1995, 378, 703–705; (c) M.
Fujita, Y. J. Kwon, S. Washizu and K. Ogura, J. Am. Chem. Soc.,
1994, 116, 1151–1152; (d ) S. Subramanian and M. J. Zaworotko,
Angew. Chem., Int. Ed. Engl., 1995, 34, 2127–2129; (e) J. S. Miller
and A. J. Spstein, Chem. Commun., 1998, 1319–1320; ( f ) M. S. E.
Fallah, E. Rentschler, A. Caneschi, R. Sessoli and D. Gatteschi,
Angew. Chem., Int. Ed. Engl., 1996, 35, 1947–1948.
ter Haar and P. Gutlich, J. Am. Chem. Soc., 1984, 106, 329–335.
´
Chem., 1997, 36, 677–683.
¨
14 R. Cortes, M. Drillon, X. Solans, L. Lezama and T. Rojo, Inorg.
15 (a) C. J. O’Connor, Prog. Inorg. Chem., 1982, 29, 203; (b) M.
Handa, Y. Sayama, M. Mikuriya, R. Nukada, I. Hiromitsu and
K. Kasuga, Bull. Chem. Soc. Jpn., 1998, 71, 119; (c) H.-Y. Shen,
W.-M. Bu, E.-Q. Gao, D.-Z. Liao, Z.-H. Jiang, S.-P. Yan and
G.-L. Wang, Inorg. Chem., 2000, 39, 396.
2
16 G. M. Sheldrick, SHELXTL97, Program for the Refinement of
Crystal Structures, University of Go¨ttingen, Germany, 1997.
894
New J. Chem., 2003, 27, 890–894