Guest-inclusion behavior of double-strand 1D coordination polymers based on N,N′-type Schiff base ligands

Article abstract of DOI:10.1002/ejic.200701106

Four double-strand one-dimensional (1D) coordination polymers, namely, {[Ni(N3Py)₂(NO₃)₂]·(C₆H ₆)_x·C₂H₅OH}_n (1), [Cd(ImBNN)₂(CH₃C

Full text of DOI:10.1002/ejic.200701106

FULL PAPER
DOI: 10.1002/ejic.200701106
Guest-Inclusion Behavior of Double-Strand 1D Coordination Polymers Based
on N,NЈ-Type Schiff Base Ligands
Qing Wang,[a] Rui Yang,[a] Chun-Feng Zhuang,[a] Jian-Yong Zhang,*[a] Bei-Sheng Kang,[a]
and Cheng-Yong Su*[a,b]
Keywords: Coordination polymers / Schiff base ligands / Double-strand chains / Crystal structures / Guest-inclusion
Four double-strand one-dimensional (1D) coordination
polymers, namely, {[Ni(N3Py)2(NO3)2]·(C6H6)x·C2H5OH}n (1),
[Cd(ImBNN)2(CH3C6H4SO3)2]n (2), {[Co(N3OPy)2(H2O)2]-
(ClO4)2·C6H6·H2O}n (3), and {[Co(N3OPy)2(H2O)2](ClO4)2·
(C8H10)x}n (4) were obtained from the assembly of three
N,NЈ-type Schiff base ligands, 1,4-bis(3-pyridyl)-2,3-diaza-
1,3-butadiene (N3Py), 2,5-bis(4Ј-(imidazol-1-yl)benzyl)-3,4-
diaza-2,4-hexadiene (ImBNN), and bis[4-(3-pyridylmethyl-
enemino)phenoxy]methane (N3OPy), with transition-metal
ions. All complexes were characterized by single-crystal X-
ray diffraction, X-ray powder diffraction, and FTIR measure-
ments. The guest-inclusion behavior of these complexes
were investigated by thermogravimetric and X-ray powder
diffraction analyses. The structural relationship between the
ligands and the cavity sizes and packing fashions have been
discussed to elucidate the distinctive guest-inclusion behav-
ior of these complexes.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
a strong inclination to interpenetrate or polycatenate with
each other,[8] thus achieving close packing to prevent for-
mation of effective channels. On the contrary, the potential
porosity that may be provided by 1D coordination poly-
mers has so far drawn little attention, although the 1D
structures have been demonstrated to be able to display di-
verse packing and interweaving modes,[9] and in some cases,
porous frameworks were afforded.[10] Since the overall
frameworks formed by the stacking of 1D polymers are es-
sentially nonrigid in contrast to the 2D and 3D coordina-
tion networks, the guest-inclusion behavior of such porous
frameworks may have the advantage of showing easy host–
guest adaptation and flexible framework shrinkage/exten-
sion depending on the guest molecules.
Introduction
In the past decades, porous coordination polymers have
attracted much attention of chemists[1,2] because these poly-
mers are able to host different guests in their cavities and
have potential properties in storage and separation.[3–5]
They also find potential applications in the adsorption of
small molecules, because the properties of the metal centres
and the size and functionality of the bridging organic li-
gands can be varied.[6,7] Many factors have been found to
influence the network and the topology of coordination
polymers, such as the coordination geometry of the metal
ions, solvents systems, counter anions, and metal-to-ligand
ratios. In principle, selection and synthesis of the organic
bridging ligands represents a key step in the design of the
architectures of the coordination polymers with specific
functionalities. By carefully modifying the size and flexibil-
ity of the ligand, numerous 1D, 2D, and 3D supramolecular
architectures have been constructed.
The N,NЈ-type Schiff base ligands have been used widely
in the field of supramolecular coordination chemistry,
affording a variety of functional 1D to 3D coordination
One of current endeavors is to synthesize longer organic
ligands with the aim to form an assembly of coordination
polymers with larger pores. However, the spacious 2D or
3D networks supported by the long spacers normally show
[a] MOE Laboratory of Bioinorganic and Synthetic Chemistry/
State Key Laboratory of Optoelectronic Materials and Technol-
ogies, School of Chemistry and Chemical Engineering, Sun Yat-
Sen University,
Guangzhou 510275, China
E-mail: cesscy@mail.sysu.edu.cn
[b] State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, China
Scheme 1. Molecular structures of the ligands.
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Guest-inclusion Behavior of Double-strand 1D Coordination Polymers
polymers, many of which are porous and able to host The different lengths and angles of the ligands lead to the
guest molecules.[11–13] Herein we report four double- formation of M2L2 basic rings with different sizes and
strand 1D coordination polymers,[14] {[Ni(N3Py)2(NO3)2]· guest-inclusion behavior.
(C6H6)x·C2H5OH}n (1), [Cd(ImBNN)2-(CH3C6H4SO3)2]n
(2), {[Co(N3OPy)2(H2O)2](ClO4)2·C6H6·H2O}n (3), and
{[Co(N3OPy)2(H2O)2](ClO4)2·(C8H10)x}n (4), which were
Results and Discussion
The ligands N3Py and ImBNN were synthesized
constructed from N,NЈ-type Schiff base ligands with dif- following literature methods by reaction of hydrazine with
ferent lengths and flexibility, namely, 1,4-bis(3-pyridyl)-2,3- 3-pyridinecarboxaldehyde or 4-(imidazol-1-yl)acetophen-
diaza-1,3-butadiene (N3Py), 2,5-bis[4Ј-(imidazol-1-yl)ben- one.[11a,12e] The ligand N3OPy was synthesized by using
zyl]-3,4-diaza-2,4-hexadiene (ImBNN), and bis[4-(3-pyr- 4,4Ј-oxydianiline and 3-pyridinecarboxaldehyde in ethanol
idylmethylenemino)phenoxy]methane (N3OPy) (Scheme 1). in the presence of a few drops of glacial acetic acid.
Table 1. Selected bond lengths [Å] and bond angles [°] for complexes 1–4.
1[a]
Ni1–O3
Ni1–N1
2.080(2)
2.117(3)
Ni1–O3(#1)
Ni1–N1(#1)
2.080(2)
2.117(3)
Ni1–N4(#2)
2.145(3)
Ni1–N4(#3)
O3–Ni1–N1
2.145(3)
O3–Ni1–O3(#1)
O3(#1)–Ni1–N1
O3(#1)–Ni1–N1(#1)
O3–Ni1–N4(#2)
N1–Ni1–N4(#2)
O3–Ni1–N4(#3)
N1–Ni1–N4(#3)
N4(#2)–Ni1–N4(#3)
180.00(9)
85.96(10)
94.04(10)
93.67(10)
93.85(10)
86.33(10)
86.15(10)
180.00(8)
94.04(10)
85.96(10)
180.00(11)
86.33(10)
86.15(10)
93.67(10)
93.85(10)
O3–Ni1–N1(#1)
N1–Ni1–N1(#1)
O3(#1)–Ni1–N4(#2)
N1(#1)–Ni1–N4(#2)
O3(#1)–Ni1–N4(#3)
N1(#1)–Ni1–N4(#3)
2[b]
Cd1–O3
Cd1–N4
Cd1–N1
O3–Cd1–O3(#1)
O3(#1)–Cd1–N4
O3(#1)–Cd1–N4(#1)
O3–Cd1–N1
2.3012(17)
2.339(2)
2.377(2)
180.00(1)
86.97(7)
93.03(7)
84.32(7)
100.03(8)
95.68(7)
79.97(8)
180.0
Cd1–O3(#1)
Cd1–N4(#1)
Cd1–N1(#1)
O3–Cd1–N4
O3–Cd1–N4(#1)
N4–Cd1–N4(#1)
O3(#1)–Cd1–N1
N4(#1)–Cd1–N1
O3(#1)–Cd1–N1(#1)
N4(#1)–Cd1–N1(#1)
2.3012(17)
2.339(2)
2.377(2)
93.03(7)
86.97(7)
180.0
95.68(7)
79.97(8)
84.32(7)
100.03(8)
N4–Cd1–N1
O3–Cd1–N1(#1)
N4–Cd1–N1(#1)
N1–Cd1–N1(#1)
3[c]
Co1–O2(#1)
Co1–N4(#2)
Co1–N1
2.1295(14)
2.1825(15)
2.1946(15)
180.00(12)
89.48(6)
90.52(6)
91.21(5)
84.32(6)
88.79(5)
95.68(6)
180.00(11)
Co1–O2
Co1–N4(#3)
Co1–N1(#1)
O2(#1)–Co1–N4(#2)
O2(#1)–Co1–N4(#3)
N4(#2)–Co1–N4(#3)
O2–Co1–N1
N4(#3)–Co1–N1
O2–Co1–N1(#1)
N4(#3)–Co1–N1(#1)
2.1295(14)
2.1825(15)
2.1946(15)
90.52(6)
89.48(6)
180.00(5)
88.79(5)
95.68(6)
91.21(5)
84.32(6)
O2(#1)–Co1–O2
O2–Co1–N4(#2)
O2–Co1–N4(#3)
O2(#1)–Co1–N1
N4(#2)–Co1–N1
O2(#1)–Co1–N1(#1)
N4(#2)–Co1–N1(#1)
N1–Co1–N1(#1)
4[d]
Co1–O2(#1)
Co1–N4(#2)
Co1–N1
2.123(2)
2.182(2)
2.193(2)
180.00(14)
89.50(9)
90.50(9)
91.16(8)
84.37(8)
88.84(8)
95.63(8)
180.00(15)
Co1–O2
Co1–N4(#3)
Co1–N1(#1)
O2(#1)–Co1–N4(#2)
O2(#1)–Co1–N4(#3)
N4(#2)–Co1–N4(#3)
O2–Co1–N1
N4(#3)–Co1–N1
O2–Co1–N1(#1)
N4(#3)-Co1–N1(#1)
2.123(2)
2.182(2)
2.193(2)
90.50(9)
89.50(9)
180.00(7)
88.84(8)
95.63(8)
91.16(8)
84.37(8)
O2(#1)–Co1–O2
O2–Co1–N4(#2)
O2–Co1–N4(#3)
O2(#1)–Co1–N1
N4(#2)–Co1–N1
O2(#1)–Co1–N1(#1)
N4(#2)–Co1–N1(#1)
N1–Co1–N1(#1)
[a] Symmetry transformations: #1: –x + 1/2, –y + 1/2, 1 –z; #2: x + 1/2, –y + 1/2, z + 1/2, #3: –x, y, –z + 1/2. [b] #1: –x, –y, –z. [c] #1:
–x, –y, –z, #2: x – 2, y – 1, z – 1, #3: 2 + x, 1 + y, 1 + z. [d] #1: –x, –y, –z, #2: x – 2, y – 1, z – 1, #3: 2 + x, 1 + y, 1 + z.
Eur. J. Inorg. Chem. 2008, 1702–1711
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FULL PAPER
Complexes 1, 2, 3, and 4 were prepared by reaction of
the corresponding metal salts with the three ligands
directly. The metal salts used are: Ni(NO3)2·6H2O,
Cd(CH3C6H4SO3)2, and Co(ClO4)2·6H2O. In general, the
solution of the metal salt was carefully layered onto the
solution of the ligand. The target crystalline complexes
formed over a period from 3 d to 2 weeks in various solvent
systems, i.e. EtOH/C6H6 for 1, EtOH/C6H6/DMF for 2,
EtOH/C6H6 for 3, and EtOH/C8H10 for 4. The presence of
ethanol as solvent in 1 and of the anions in 1–4 were con-
firmed by their characteristic IR absorption bands
–
[3360 cm–1 for ethanol; 1384 cm–1 and 1314 cm–1 for NO3 ;
–
1176 cm–1, 1035 cm–1, and 1011 cm–1 for CH3C6H4SO3 ;
1038 cm–1 and 1012 cm–1 for ClO4– in complex 3; 1102 cm–1
–
for ClO4 in complex 4]. All samples seem to be moisture
sensitive and varied amounts of water molecules were ad-
sorbed when the samples were kept in air, which resulted in
slightly different compositions to those of the single-crys-
tals, as seen from the elemental analyses results.
Complex 1 was prepared from the rigid, linear ligand
N3Py and Ni(NO3)2·6H2O. X-ray crystallographic analysis
reveals that it is a double-strand 1D chain. The NiII ion
lying on an inversion centre is hexacoordinate with four N-
donor atoms from four different N3Py ligands, with N–Ni–
N bond angles of 86.15(10), 93.67(10), and 180.00(11)° and
Ni–N bond lengths of 2.117(3) and 2.145(3) Å. The two
axial positions are occupied by two O-donor atoms from
two nitrate ions, with an O–Ni–O bond angle of 180.00(9)°
and a Ni–O bond length of 2.080(2) Å (Table 1). Thus, the
central metal ion NiII adopts an octahedral geometry (Fig-
ure 1a). Each N3Py ligand links two metal ions to generate
the infinite, double-strand 1D chain containing 22-mem-
bered M2L2 repeating rings. The Ni···Ni distance within the
M2L2 basic ring is 11.9 Å and the N2···N3 distance is 5.3 Å,
which define the size of the M2L2 ring (Figure 1b).
Figure 1. (a) Molecular structure of complex 1 with atomic label-
ling scheme; (b) M2L2 basic rings; (c) guest-filled crystal packing
of the 1D chains with a space-fill model for the benzene molecules
in complex 1.
–
In complex 1, no guest molecule is hosted inside the basic pied by two O-donor atoms from two CH3C6H4SO3 ions,
M2L2 ring. This may be due to the rigidity of the linear with a O–Cd–O bond angle of 180.000(1)° and a Cd–O
ligand and the “V” shape of the M2L2 ring, which cannot bond length of 2.3012(17) Å (Figure 2a). The ImBNN li-
provide a suitable host environment for the guests. Instead, gands link the metal ions to generate an infinite double-
waving channels are present between adjacent double- strand 1D chain containing repeating 38-membered M2L2
strand chains in the a direction, in which benzene and etha- macrocyclic rings with the size of 21.1ϫ4.1 Å, which is de-
nol molecules are enclosed (Figure 1c). Therefore, the crys- fined by the Cd···Cd distance versus the N3···N3 distance
tal packing in complex 1 can be regarded to form 2D in- within the M2L2 basic ring (Figure 2b).
tercalated layers in the ac plane, with alternate stacking of
As expected, a much longer M2L2 ring was formed in
the coordination chains and host molecules along the b di- complex 2 than in complex 1. The length is almost twice as
rection. Guest molecules of benzene and ethanol interact long (21.1 versus 11.9 Å), but the width of the M2L2 ring
with the double-strand chains through π···π stacking and is slightly reduced (4.1 versus 5.3 Å). The two ligands are
C–H···O hydrogen-bonding interactions.
aligned nearly in a parallel fashion, which prevents accom-
To create a larger M2L2 basic ring, the ligand ImBNN modation of any guest molecules inside such a compressed
was prepared, which is structurally similar to N3Py but long and narrow space. Similar to that in complex 1, a lay-
longer. Reaction of ImBNN with Cd(CH3C6H4SO3)2 af- ered packing fashion is observed in 2, and apparent chan-
forded complex 2. X-ray crystallographic analysis shows nels are formed in the a direction because of the weaving
that complex 2 has a similar double-strand 1D chain struc- arrangement of the 1D chain. However, bulky
ture. The CdII ion adopts the same octahedral geometry CH3C6H4SO3– anions occupy the channels, which leaves no
and is coordinated by four N-donor atoms from four dif- space to host any guest molecules inside the channel. The
ferent ImBNN ligands, with N–Cd–N bond angles of adjacent double-strand chains are packed tightly by form-
79.97(8), 100.03(8), and 180° and Cd–N bond lengths of ing π···π stacking interactions between the ligands and C–
2.339(2) and 2.377(2) Å. The two axial positions are occu- H···O interactions between anions and ligands (Figure 2c).
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Guest-inclusion Behavior of Double-strand 1D Coordination Polymers
Figure 2. (a) Molecular structure of complex 2 with atomic labeling
scheme; (b) M2L2 basic rings; (c) crystal packing of the 1D chains
in complex 2.
Figure 3. (a) Molecular structures of complexes 3 and 4 with
atomic labelling scheme; (b) guest-filled crystal packing of the 1D
chains in the c direction, showing inclusion of benzene molecules
inside the M2L2 basic rings in 3; (c) channels formed in 3 in the a
direction, in which benzene guest molecules are shown in space-
filling mode.
It is noticeable from complexes 1 and 2 that the rigid
ligands are not good candidates for fabrication of double-
strand chain structures containing M2L2 ring units with ef-
fective voids to host guest molecules. To modify the ligand
structure, we prepared the long angular ligand N3OPy,
which possesses an ether O atom to allow two rigid Schiff in Figure 3b. The solvated water molecules and ClO4
base arms to make an angle. Reaction of this ligand with anions are located between the double-strand chains, and
Co(ClO4)2·6H2O gave complex 3, which shows a similar π···π stacking between the ligands and C–H···O hydrogen
–
–
double-strand 1D structure as in 1 and 2 (Figure 3a). The bonds between ClO4 or water and the ligands are formed.
central CoII ion also adopts an octahedral geometry by The double-strand chains can be considered to align paral-
binding four N-donor atoms from four N3OPy ligands, lelly in the bc direction to form layers as depicted in Fig-
with N–Co–N bond angles of 84.32(6), 95.68(6), and ure 3c. Channels are formed in the a direction, in which
180.00(11)° and Co–N bond lengths of 2.1825(15) and benzene guest molecules are accommodated. Such a chan-
2.1946(15) Å. The two axial positions are occupied by O- nel, which has a layered packing fashion, is apparently dif-
donor atoms from two solvated water molecules, with a O– ferent from those in complexes 1 and 2, which show inter-
Co–O bond angle of 180.00(12)° and a Co–O bond length calation of the guest in between the coordination layers.
of 2.1295(14) Å.
Complex 4 has actually an analogous structure to that
Since the ligand N3OPy is angular (the ЄC–O–C angle of 3 as they have the same coordination framework and
is about 120°), the M2L2 basic ring in complex 3 is confor- similar M2L2 basic rings with the size of about
mationally distinct from those in complexes 1 and 2. The 20.1ϫ12.1 Å, as shown in Figure 4. Instead of the benzene
four rigid Schiff base arms of the two ligands constitute the molecules, m-xylene guest molecules are located within the
four edges and the two CoII ions and two O atoms can be M2L2 basic rings, which form the same channels in the a
regarded as the vertices. The size of the thus formed rhom- direction in the crystal lattice. This finding indicates that
bic ring is about 20.1ϫ12.2 Å, which is estimated by the the [Co(N3OPy)2(H2O)2]2+ coordination framework in both
separation of Co···Co and O1···O1. Therefore, the M2L2 3 and 4 can provide robust cavities to accommodate guest
ring in 3 is large enough to host a benzene guest as shown molecules with similar polarity and structural natures.
Eur. J. Inorg. Chem. 2008, 1702–1711
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FULL PAPER
Figure 6. X-ray powder diffraction patterns of complex 2: (a) simu-
lated and (b) measured.
To study the guest-inclusion behavior of the guest-con-
taining complexes 1, 3, and 4, TGA and XRD measure-
ments were performed separately for the as-prepared sam-
ples, solvent-free samples obtained upon heating at certain
temperatures, and samples after readsorbing guest mole-
cules.
The TG curve of the fresh sample of complex 1 shows a
weight loss of 25.7% in the temperature range 20–195 °C,
which corresponds to the loss of one ethanol molecule and
two benzene molecules per formula unit (calculated 25.1%).
The coordination framework of complex 1 collapses in the
range 190–420 °C (Figure 7a). The solvent-free sample
([Ni(N3Py)2(NO3)2]n (denoted as complex 1Ј) was obtained
by heating a crystalline sample of complex 1 to 100 °C for
5 h in air. The TG analysis of 1Ј shows no weight loss before
200 °C, which indicates that all guest molecules had evapo-
rated. A similar weight loss pattern was observed from 200–
420 °C as in 1, which indicates the decomposition of the
coordination framework (Figure 6b). By dipping solvent-
free sample 1Ј in benzene for 2 d, complex 1ЈЈ was obtained.
The TG analysis of 1ЈЈ shows a weight loss of 10.8% in the
temperature range 30–220 °C, which corresponds to the loss
of approximately one benzene molecule per formula unit
(expected 11.4%) [Figure 6c]. This finding suggests that the
“dry” complex 1Ј can readsorb about one benzene molecule
Figure 4. (a) Guest-filled crystal packing of the 1D chains in the c
direction, showing inclusion of m-xylene molecules inside the M2L2
basic rings in 4; (b) Channels formed in 4 in the a direction, where
m-xylene guest molecules are shown in space-filling mode.
Guest Inclusion Behavior
As discussed above, X-ray single-crystal diffraction
analysis indicates that complex 2 contains no solvated mole-
cules. However, thermogravimetric analyses (TGA) of com-
plex 2 gives a curve showing a small gradual weight loss,
which suggests that the sample is moisture sensitive (Fig-
ure 5). The coordination framework of complex 2 collapses
in the temperature range 300–660 °C. X-ray powder diffrac-
tion (XRD) analysis of the bulk sample shows a pattern
that closely matches the simulated one, which is indicative
of the pure solid-state phase (Figure 6).
Figure 7. TG curves for the complexes: (a) as-prepared {[Ni(N3Py)2-
(NO3)2]·(C6H6)2·C2H5OH}n (1); (b) solvent-free [Ni(N3Py)2-
(NO3)2]n (1Ј); (c) after the guest molecule is readsorbed,
{[Ni(N3Py)2(NO3)2]·C6H6}n (1ЈЈ).
Figure 5. TG curve for complex 2.
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Guest-inclusion Behavior of Double-strand 1D Coordination Polymers
to give a complex 1ЈЈ with the formula [Ni(N3Py)2(NO3)2]· 250–600 °C (Figure 9b), and this is consistent with the col-
C6H6, but is not able to revert to complex 1 completely.
lapse of the guest-inclusion sample. After sample of 3Ј was
It was found that fresh crystals of complex 1 lose their dipped in benzene for 2 d, complex 3ЈЈ was obtained. The
transparency quickly after leaving the mother liquid. This TG analysis shows a weight loss of 12.8% in the tempera-
means that the solvated molecules may escape partially in ture range 30–250 °C, which corresponds to the loss of two
air, which usually causes changes in the crystal structure. benzene molecules per formula unit (expected 12.9%, Fig-
Indeed, the XRD measurement of the opaque sample re- ure 9c). This means that the guest-free complex 3Ј can read-
veals significant variations in the intensity of some peaks sorb twice the number of benzene guest molecules than
(Figure 8b) relative to the pattern simulated from the single- those contained in complex 3. In the temperature range
crystal diffraction data (Figure 8a). After all guest mole- 300–600 °C, the decomposition behavior of the coordina-
cules from the crystals are released by heating, the XRD tion framework of the sample in which the guest molecules
analysis was performed for complex 1Ј. As shown in Fig- are readsorbed remains rather similar to that of complex 3.
ure 8c, the resulting pattern exhibits new distinctive fea-
tures, which may suggest further structural transformation.
The XRD pattern of the readsorbed sample 1ЈЈ (Figure 8d)
resembles that of 1Ј, but a few peaks are shifted in position
and vary in intensity.
Figure 9. TG curves for the complexes: (a) as-prepared
{[Co(N3OPy)2(H2O)2](ClO4)2·C6H6·H2O}n (3); (b) solvent-free
{[Co(N3OPy)2(H2O)2](ClO4)2}n (3Ј); (c) after the guest molecules
are readsorbed, {[Co(N3OPy)2(H2O)2](ClO4)2·(C6H6)2}n (3ЈЈ).
Figure 8. (a) Simulated X-ray powder diffraction pattern of com-
plex 1. Measured X-ray powder diffraction patterns: (b) as-pre-
pared sample of complex 1; (c) solvent-free complex 1Ј; (d) after
the guest molecule is readsorbed, complex 1ЈЈ.
The single crystals of complex 3 rapidly crack when ex-
The above observations indicate that the crystal structure posed to air, which is indicative of the partial escape of the
of complex 1 is subject to subtle changes in the solvated guest molecules from the crystal lattice. The XRD pattern
molecules. As the guest molecules leave and re-enter, crys- of such a sample displays small shift in the position of some
tal-to-crystal phase transformation occurs. This is expected of the peaks relative to those in the simulated pattern of the
because complex 1 has intercalated packing layers in the single crystal (Figure 10a and 10b). When all the solvated
crystal lattice. Movement of the solvent may easily trigger molecules are completely removed by heating, the XRD
sliding of the double-strand chain layers, which will result pattern of the solvent-free complex 3Ј maintains the main
in alteration of the unit cell parameters. However, since the profile of the guest-inclusion complex 3. However, a few
overall coordination framework has a relatively high ther- new peaks appear, and the intensity of some of the peaks
mostability (around 200 °C), desorption and readsorption alters (Figure 10c). After readsorption of benzene guest
of guest molecules only leads to crystal-to-crystal phase molecules, complex 3ЈЈ gives rise to an XRD pattern that
change without collapse of the crystal lattice completely. resembles the simulated pattern (Figure 10d). These find-
Readsorption of the guest molecules is obviously not com- ings suggest that the crystal packing in complex 3 is more
plete, and the solid-state phase change is not reversible.
tolerant towards the desorption and re-adsorption of guest
The TG curve for complex 3 shows a weight loss of 8.0% molecules than that in complex 1. From the structural
in the temperature range 30 –200 °C, which corresponds to analysis, we can see that, in contrast to complex 1, the lay-
the loss of one water molecule and one benzene molecule ered packing in complex 3 is independent of the type of
(calculated 8.4%) per formula unit. This suggests evapora- guest molecules. The guest molecules can move along the
tion of all solvent molecules. The coordination framework channels that are formed by the M2L2 rings within the
collapses in the range 280–600 °C (Figure 9a). Complex 3Ј double-strand 1D chains. Therefore, the desorption and re-
was obtained after heating the crystalline sample of com- adsorption of guest molecules is not expected to show a
plex 3 to 100 °C for 5 h in air. The TG analysis confirms significant influence on the overall crystal lattice. The XRD
that there is no weight loss before 250 °C, which indicates results indicate that slight crystal-to-crystal phase transfor-
that there are no benzene and water molecules retained in mation occurs during the movement of the guest molecules;
3Ј. The coordination framework of 3Ј collapses in the range however, the crystal framework is almost restored after de-
Eur. J. Inorg. Chem. 2008, 1702–1711
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1707

Q. Wang, R. Yang, C.-F. Zhuang, J.-Y. Zhang, B.-S. Kang, C.-Y. Su
FULL PAPER
sorbing and then readsorbing of the guest molecules, even
after twice the amount of the benzene guest molecules is
readsorbed. This confirms the permanence of the porous
framework in complex 3, which is in agreement with the
TGA results and the structural analysis.
Figure 11. TG curves for the complexes: (a) as-prepared
{[Co(N3OPy)2(H2O)2](ClO4)2·C8H10}n (4); (b) solvent-free
{[Co(N3OPy)2(H2O)2](ClO4)2}n (4Ј); (c) after the guest molecule is
readsorbed, {[Co(N3OPy)2(H2O)2](ClO4)2·C8H10}n (4ЈЈ).
Figure 10. (a) Simulated X-ray powder diffraction pattern of com-
plex 3. Measured X-ray powder diffraction patterns: (b) as-pre-
pared sample of complex 3; (c) solvent-free complex 3Ј; (d) after
the guest molecules are readsorbed, complex 3ЈЈ.
ure 12a and 12b). The XRD pattern of the solvent-free
complex 4Ј is slightly different with the appearance of a few
small peaks (Figure 12c). After readsorption of the guest
molecule, the XRD pattern of complex 4ЈЈ retains the major
pattern profile of that of complex 4, but complex 4 does
not seem to be recovered completely (Figure 12d). These
observations suggest that a fine crystal-to-crystal phase
change accompanies the desorption and readsorption pro-
cess of the guest molecules; however, the main crystal
framework is well supported by the layered 1D coordina-
tion polymers. The channels formed by the double-stand
chains allow the movement of larger guest molecules (m-
xylene in 4 versus benzene in 3), but may have more interac-
tions with the guests.
The TG curve of complex 4 shows a weight loss of 9.9%
in the temperature range 30–160 °C, which can be assigned
to the loss of one m-xylene molecule per formula unit (cal-
culated 9.2%). In addition, a small weight loss of about
3.3% in the temperature range 160–205 °C appears. This
may be attributed to the loss of two coordination water
molecules (calculated 3.1%), followed by complete collapse
of the coordination framework from 270 to 650 °C (Fig-
ure 11a). The solvent-free complex 4Ј was obtained by heat-
ing a crystalline sample of complex 4 to 150 °C for 15 h in
air. The TG analysis shows no weight loss before 160 °C,
which suggests that there is no remaining m-xylene mole-
cule in 4Ј. From 160 to 600 °C, the sample 4Ј displays a
similar coordination-framework decomposition process to
that of the guest-inclusion complex 4 (Figure 11b). After 4Ј
was dipped in m-xylene for 2 d, complex 4ЈЈ was obtained.
The TG analysis shows a gradual weight loss of 9.6% in
the temperature range 30–180 °C, which corresponds to the
loss of one m-xylene molecule per formula unit (expected
9.2%). Thereafter, the coordination framework decomposes
in a similar way to that of complex 4, although the final
temperature is lower, before 550 °C (Figure 11c). These re-
sults indicate that the guest molecules in complex 4 can be
removed and readsorbed, but m-xylene guest molecules
cannot be readsorbed as much as the guest molecules in 3.
The host framework displays a more complicated interac-
tion with the guest molecules relative to that in complex 3.
This means that the absence of guest water molecules and
the slightly different molecular structure of m-xylene guest
molecules in complex 4 may impart a delicate influence on
the guest-inclusion behavior relative to that of complex 3.
Figure 12. (a) Simulated X-ray powder diffraction pattern of com-
plex 4. Measured X-ray powder diffraction patterns: (b) as-pre-
pared sample of complex 4; (c) solvent-free complex 4Ј; (d) after
the guest molecule is readsorbed complex 4ЈЈ.
Conclusions
Four double-strand 1D coordination polymers were pre-
pared by using three Schiff base N,NЈ-type ligands, N3Py,
The solid-state phase information during the desorption ImBNN, and N3OPy, with varied spacer lengths and struc-
and readsorption of the guest molecules has been checked tural flexibility. The single-crystal structural analyses indi-
by XRD measurements. The as-prepared sample of com- cate that the size and shape of the common M2L2 basic
plex 4 exhibits an XRD pattern that closely matches the rings in these complexes are different because of the dif-
simulated pattern from the single-crystal analysis (Fig- ferent nature of the ligands. In complexes 1 and 2, the M2L2
1708
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 1702–1711

Guest-inclusion Behavior of Double-strand 1D Coordination Polymers
(s), 1326 (s), 1283 (s), 1186 (s), 1102 (s), 977 (m), 845 (s), 700.89
(s), 541 (s) cm–1. C24H18N4O (378.4): calcd. C 76.16, H 4.80, N
14.81; found C 76.41, H 4.90, N 14.62.
rings do not afford effective voids to accommodate the
guest molecules because of the linear rigidity of the N3Py
and ImBNN ligands. An intercalated layering crystal pack-
ing fashion is observed in complexes 1 and 2; complex 1
hosts guest molecules in between the adjacent double-
{[Ni(N3Py)2(NO3)2]·(C6H6)x·C2H5OH}n
(1):
Ni(NO3)2·6H2O
(29 mg, 0.10 mmol) was dissolved in ethanol (3 mL) and then care-
fully layered onto a solution of N3Py (42 mg, 0.20 mmol) in C6H6
(4 mL). After three days, green block crystals suitable for single-
crystal X-ray analysis formed at the interface of the two solutions.
strand 1D chains, while complex
2 contains bulky
counteranions that occupy the apparent channels. Larger
M2L2 rings are formed by using the long angular N3OPy
ligand in complexes 3 and 4, which afford spacious voids
to host benzene or m-xylene guest molecules. In addition,
these M2L2 rings constitute a 1D channel through parallel
alignment of the double-strand chains in the crystal lattice
in 3 and 4. This results in permanent porosity after removal
of the guest molecules. The study of the guest-inclusion be-
havior of complexes 1, 3, and 4 indicates that crystal-to-
crystal phase transformation is accompanied with desorp-
tion and readsorption of the guest molecules. A significant
solid-state phase change is observed in complex 1 during
the movement of the guest molecule, which is inherent to
its intercalated layering packing fashion. On the contrary,
complexes 3 and 4 have more robust porous frameworks,
which facilitate complete guest desorption and readsorp-
tion. However, although the complexes 3 and 4 contain the
same host frameworks, they display adaptive guest-in-
clusion behavior towards different guest molecules. For
complex 3, twice the amount of benzene guest molecules
can be readsorbed by the guest-free complex without re-
markable change of the crystal framework, while for com-
plex 4, the m-xylene guest molecules noticeably interact
with the host framework and the same amount of guest
molecules are readsorbed after removal.
Yield 48 mg (60%) based on the ligand. IR (KBr): ν = 3360 (m),
˜
1630 (s), 1607 (w), 1415 (m), 1384 (s), 1314 (m), 1192 (w), 1106
(w), 1035 (w), 973 (w), 956 (w), 878 (w), 821 (w), 704 (m), 687 (m),
645 (w), 420 (w) cm–1. C32H36N10NiO9 (1·2H2O, x = 1, 763.38):
calcd. C 50.35, H 4.75, N 18.35; found C 50.42, H 4.45, N 18.74.
[Cd(ImBNN)2(CH3C6H4SO3)2]n (2): Cd(CH3C6H4SO3)2 (23 mg,
0.05 mmol) was dissolved in ethanol (3 mL) and then carefully lay-
ered onto a solution of ImBNN (19 mg, 0.05 mmol) in C6H6 and
DMF (2:1, 3 mL). After about two weeks, yellow block crystals
suitable for single-crystal X-ray analysis formed at the interface of
the two solutions. Yield 15 mg (50%) based on the ligand. IR
(KBr): ν = 3123 (m), 1604 (s), 1520 (s), 1488 (m), 1362 (m), 1306
˜
(m), 1247 (s), 1176 (s), 1120 (s), 1060 (m), 1035 (m), 1011 (m), 962
(w), 921 (w), 830 (s), 752 (w), 681 (m), 568 (m) cm–1.
Cd0.5C29H27N6O3S (595.83): calcd. C 58.46, H 4.57, N 14.10; found
C 58.30, H 4.62, N 13.90.
{[Co(N3OPy)2(H2O)2](ClO4)2·C6H6·H2O}n (3): Co(ClO4)2·6H2O
(19 mg, 0.05 mmol) was dissolved in ethanol (3 mL) and then care-
fully layered onto a solution of N3OPy (38 mg, 0.10 mmol) in C6H6
(8 mL). After about two weeks, brown block crystals suitable for
single-crystal X-ray analysis formed at the interface of the two solu-
tions. Yield 17 mg (30%) based on the ligand. IR (KBr): ν = 3421
˜
(m), 1626 (s), 1494 (s), 1429 (w), 1239 (s), 1120 (s), 837 (m), 703
(m), 625 (m), 419 (w) cm–1. C54H50Cl2CoN8O14 (3·H2O, 1164.86):
calcd. C 55.68, H 4.33, N 9.62; found C 55.64, H 4.03, N 9.70.
{[Co(N3OPy)2(H2O)2](ClO4)2·(C8H10)x}n (4): Co(ClO4)2·6H2O
(19 mg, 0.05 mmol) was dissolved in ethanol (3 mL) and then care-
fully layered onto a solution of N3OPy (38 mg, 0.10 mmol) in m-
xylene (8 mL). After about two weeks, brown block crystals suit-
able for single-crystal X-ray analysis formed at the interface of the
two solutions. Yield 17 mg (30%) based on the ligand. IR (KBr):
Experimental Section
Materials and Methods: All starting materials and solvents were
obtained from commercial sources and used without further purifi-
cation. The ligands N3Py and ImBNN were synthesized following
literature methods.[11a,12e] Infrared spectra were measured on a Nic-
olet/Nexus-670 FTIR spectrometer with KBr pellets. X-ray powder
diffraction data was recorded on a Bruker D8 Advance dif-
fractometer at 40 kV, 40 mA with a Cu-target tube and a graphite
monochromator. Thermogravimetric analysis (TGA) was per-
formed in air and under 1 atm. of pressure at a heating rate of
10 °C/min on a NETZSCH Thermo Microbalance TG 209 F3 Tar-
sus.
ν = 3415 (s), 1627 (m), 1494 (s), 1426 (m), 1329 (w), 1284 (w), 1238
˜
(s), 1202 (m), 1102 (s), 8407 (m), 704 (m), 624 (m), 545 (w) cm–1.
C52H49Cl2CoN8O14 (4·2H2O, x = 0.5, 1158.26): calcd. C54.79, H
4.33, N 9.83; found C 55.11, H 4.37, N 9.51.
X-ray Structure Analyses: The intensity data of complex 1 was col-
lected on an Enraf Nonius CAD4 four-cycle diffractometer (Mo-
Kα radiation, λ = 0.71073 Å) equipped with a graphite crystal mon-
ochromator situated in the incident beam. The unit cell parameters
were determined by least-squares refinement by using the setting
2θ angles of 25 carefully centered reflections. The reflections of
complex 2 were collected on an Oxford Gemini S Ultra dif-
fractometer and those of complexes 3 and 4 were collected on a
Bruker Smart 1000 CCD diffractometer equipped with graphite
monochromated Mo-Kα radiation (λ = 0.71073 Å). The structures
were solved by direct methods followed by difference Fourier syn-
theses and refined by the full-matrix least-squares method against
Syntheses
N3OPy: 4,4Ј-Oxydianiline (2 g, 10 mmol) and 3-pyridinecarboxal-
dehyde (1.95 mL, 20 mmol) were mixed in ethanol (80 mL). After
addition of eight drops of glacial acetic acid, the mixture was
heated at reflux for 24 h. The solution was slowly evaporated to
near dryness under reduced pressure, and subsequently cooled to
room temperature, after which a white precipitate was obtained.
After recrystallization from hot ethanol, the white product was har-
vested. Yield: 2.70 g (71%). 1H NMR (300 MHz, CDCl3, 25 °C): δ
2
Fo with the SHELXTL software.[15] The coordinates of the non-
hydrogen atoms were refined anisotropically except for those ex-
plained below. All hydrogen atoms were introduced in calculated
positions. In complex 1, the solvated ethanol molecules are disor-
dered over two positions. The solvated water molecule in complex
3 is distributed over two sites, which were assigned half occupancy
without addition of the hydrogen atoms. The benzene molecules
3
= 9.01 (s, 2 H, Py-H), 8.69–8.71 (d, J = 4.5 Hz, 2 H, Py-H), 7.41–
7.45 (dd, 3J = 4.8, 3J = 7.8 Hz, 2 H, Py-H), 8.29–8.31 (d, 3J =
7.8 Hz, 2 H, Py-H), 8.54 (s, 2 H, –CH=N), 7.26–7.29 (d, 3J =
8.7 Hz, 4 H, Ph-H), 7.06–7.09 (d, 3J = 8.7 Hz, 4 H, Ph-H) ppm.
IR (KBr): ν = 3056 (m), 2880 (m), 1622 (s), 1588 (s), 1496 (s), 1419
˜
Eur. J. Inorg. Chem. 2008, 1702–1711
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1709

Q. Wang, R. Yang, C.-F. Zhuang, J.-Y. Zhang, B.-S. Kang, C.-Y. Su
FULL PAPER
Table 2. Crystallographic data for complexes 1–4.
1
2
3
4
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C38H38N10NiO7
805.49
monoclinic
C2/c
10.772(2)
16.887(3)
23.130(5)
90
99.98(3)
90
C29H27Cd0.5N6O3S
595.83
C54H48Cl2CoN8O13
1146.83
C56H5 °Cl2CoN8O12
1156.87
triclinic
triclinic
triclinic
¯
¯
¯
P1
P1
P1
9.8714(13)
9.9271(19)
14.797(3)
87.270(16)
71.388(15)
74.944(14)
1326.0(4)
0.40ϫ0.35ϫ0.30
2
1.492
0.556
150(2)
0.0287
9.9034(11)
12.5021(14)
12.8784(15)
112.282(2)
109.017(2)
92.466(2)
1369.4(3)
0.45ϫ0.39ϫ0.30
1
1.391
0.482
150(2)
0.0211
9.8175(11)
12.4818(14)
12.8567(14)
111.215(2)
109.160(2)
92.401(2)
1364.0(3)
0.32ϫ0.25ϫ0.12
1
1.408
0.483
150(2)
0.0155
α [°]
β [°]
γ [°]
V [Å3]
4143.8(14)
Crystal dimensions [mm] 0.60ϫ0.40ϫ0.30
Z
4
ρcalcd. [gcm–3]
µ [mm–1]
T [K]
1.291
0.526
293(2)
0.0174
0.0537
0.1359
1.038
R(int)
R1[IϾ2σ(I)]
wR2[IϾ2σ(I)]
S
0.0367
0.1018
1.030
0.0546
0.1573
1.073
0.0535
0.1498
1.037
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show severe disorder in two adjacent positions and were modeled
by the AFIX 66 restraint in the refinement. In complex 4, the m-
xylene guest molecules are also badly disordered over two posi-
tions. The same model was applied as in complex 3, and all carbon
atoms were refined isotropically. Crystallographic data and other
pertinent information for complexes 1–4 are summarized in
Table 2. CCDC-660473, -660474, -660475 and -660476 contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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