The effect of the conformation of flexible carboxylate ligands on the structures of metal-organic supramolecules

Article abstract of DOI:10.1039/c0nj00328j

Three flexible bent dicarboxylate ligands, 2,2′-(2,3,5,6-tetramethyl- 1,4-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H₂L ¹), 2,2′-(1,4-phenylenebis(methylene))bis(sulfanediyl)dibenzoic acid (H₂L⁹) a

Full text of DOI:10.1039/c0nj00328j

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PAPER
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The effect of the conformation of flexible carboxylate ligands on the
structures of metal–organic supramoleculeswz
Fangna Dai,a Shuwen Gong,b Peipei Cui,a Guoqing Zhang,a Xiaoliang Qiu,a
Fei Ye,a Daofeng Sun,*a Zhijian Pang,a Lei Zhang,a Guilin Donga and
Changqiao Zhang*a
Received (in Montpellier, France) 29th April 2010, Accepted 26th July 2010
DOI: 10.1039/c0nj00328j
Three flexible bent dicarboxylate ligands, 2,20-(2,3,5,6-tetramethyl-1,4-phenylene)-
bis(methylene)bis(sulfanediyl)dibenzoic acid (H2L1), 2,20-(1,4-phenylenebis(methylene))-
bis(sulfanediyl)dibenzoic acid (H2L9) and 2,20-(2,3,5,6-tetramethyl-1,4-phenylene)bis-
(methylene)bis(oxy)dibenzoic acid (H2L10), have been designed and synthesized. The positions of
the functional substituents are in 1,4-positions of the central benzene ring, and all the ligands can
adopt syn and anti conformations. By applying these flexible ligands to assemble with thulium
ions or zinc ions, three metal–organic supramolecules with metallamacrocycles or 1D chains have
been isolated. L1 adopts a syn conformation in complex 1, leading to a 0D metallamacrocycle,
L9 in complex 2 adopts an anti conformation to form a 1D ‘‘rainbow-like’’ chain while L10 in
complex 3 adopts both syn and anti conformations. L10 in a syn conformation connects
Zn4(OH)2(CO2)4 SBU to form a 0D metallamacrocycle, which is further connected by the ligand
in an anti conformation to generate a 1D coordination polymer.
MOFs. Tong et al.8 have synthesized nanoscale cages based on
conformationally-flexible cyclohexanehexacarboxylate. Zheng,
Introduction
Batten and Hong et al.9 have reported new compounds built
from long flexible multicarboxylate ligands and tested their
The rational design and synthesis of metal–organic frameworks
(MOFs) with various configurations or multi-dimensional
open frameworks has attracted much attention from chemists
physical properties, respectively. One of the hot topics is to
due to their interesting structural topologies and potential
applications in catalysis, separation and gas storage, etc.1–3 In
study the effect of the conformation of flexible ligands, syn or
anti, on structural topologies.10,11
general, the starting materials, such as in the conformation of
Recently, we have designed a series of flexible bent dicarbo-
xylate ligands12 for the construction of discrete cages or
the organic ligand, can determine the structure of the final
product. Hence, it is possible to predict the final structure
cage-containing MOFs, in which the flexible bent dicarboxylate
when some simple ligands are used, especially for rigid and
small ligands.4 In contrast to rigid ligands with single
ligands are apt to adopt a syn conformation. Both syn and anti
conformations co-existing in one complex are still rare in the
conformations, flexible ligands may adopt several kinds of
reported work.
conformation when they coordinate to metal ions, complicating
the prediction of the final products.5
The difficulty of structural prediction has probably stimulated
In this paper, we focus our attention on the construction of
metal–organic supramolecules based on flexible dicarboxylate
ligands and study the effect of their conformation on the
researchers’ interests in the design and synthesis of MOFs
final structures of the products. Three ditopic ligands
employing flexible ligands to explore the relationships between
the conformation of the ligand and the final structure.6 On the
endow flexibility to the whole ligand, have been applied in
possessing –CH2–S– spacers or –CH2–O– spacers, which
other hand, flexible ligands in the construction of MOFs may
generate novel complexes with interesting topologies and
attractive properties. In particular, Allendorf et al.7 have
reported the design and synthesis of luminescent stilbene-based
this work. By the self-assembly of these ligands with metal ions,
three metal–organic supramolecules, Tm2(L1)2(dmf)4(NO3)2(1),
[Zn(L9)(phen)]ꢀ4H2O (2) and [Zn4(L10)3(m3-OH)2(H2O)2]ꢀ
2H2Oꢀ2EtOH (3) have been isolated, with the 0D
metallamacrocycle of 1 based on a syn-L1 ligand, the 1D
‘‘rainbow-like’’ zig-zag chain of 2 based on an anti-L9 ligand
and the 1D Zn4(OH)2(CO2)4-based chain of 3 based on both
syn- and anti-L10 ligands (Scheme 1).
a Key Lab for Colloid and Interface Chemistry of Education Ministry,
Department of Chemistry, Shandong University, Jinan 250100,
P. R. China. E-mail: dfsun@sdu.edu.cn, zhangchqiao@sdu.edu.cn;
Fax: +86 53188364218; Tel: +86 53188364218
b Department of Chemistry, Liaocheng University, Liaocheng, 252059,
P. R. China
Results and discussion
w This article is part of a themed issue on Coordination polymers:
structure and function.
Syntheses
z Electronic supplementary information (ESI) available: Structural
figures and TGA data for complexes 1–3. CCDC 775311–775313.
For crystallographic data in CIF or other electronic format see DOI:
10.1039/c0nj00328j
As mentioned above, the conformation of the organic ligand
plays important roles in the final architecture. We have studied
c
2496 New J. Chem., 2010, 34, 2496–2501 This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2010

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Scheme 1 The flexible carboxylate ligands used in this work and the
subunits (a, b) formed by flexible ligands with a syn-conformation
(red) and an anti-conformation (black).
the relationships between the conformation of the ligand and
the structure of the final product when the positions of the
functional substituents are changed from 1,2- and 1,3- to the
1,4-positions of the central benzene ring, providing different
geometries of the carboxylate ligands.12b In this work, we
focus our attention on introducing functional groups into
the 1,4-positions due to its minimal steric hindrance. The
organic ligands were synthesized according to the literature.13
In different conditions, a 1,4-substituted ligand coordinating
with appropriate coordination geometry metal ions will give
plentiful frameworks, such as 0D discrete molecules or 1D
supramolecular chains by adopting syn- or anti-conformations
(Scheme 2). By the self-assembly of flexible dicarboxylate
ligands with thulium ions or zinc ions, three metal–organic
supramolecules have been synthesized.
Fig. 1 (a) and (b): The rectangular metallamacrocycle of 1. (c): The
2D layer formed by pꢀ ꢀ ꢀp interactions.
from two coordinated dmf molecules and one coordinated
nitrate ion with an average Tm–O distance of 2.326 A. Both
carboxylate groups of the L1 ligand adopt a chelating mode to
connect one Tm ion. The average dihedral angle between the
side benzene ring and the central benzene ring is 89.81.
Thus, two Tm ions are connected by two L1 ligands to
generate a rectangular metallamacrocycle with dimensions of
13.40 ꢁ 8.61 A (Fig. 1a and b). The remaining coordination
sites of the Tm ion are occupied by coordinated solvates and
ꢂ
the NO3 anion to prevent further extension. The metalla-
Metallamacrocycle of complex 1. Single-crystal X-ray
diffraction reveals that complex 1 is a rectangular macrocycle
made up of two L1 ligands and two thulium ions. The
asymmetric unit of 1 consists of one thulium ion, one L1
ligand, two coordinated dmf molecules and one coordinated
nitrate ion. There is only half a complex in the asymmetry unit,
the other part is generated by an inversion centre. The central
Tm ion, which lies about an inversion centre, is eight-coordinated
by four oxygen atoms from two L1 ligands, four oxygen atoms
macrocycles are further connected to one another through
pꢀ ꢀ ꢀp interactions between the side benzene rings of L1 ligands
in different molecules to generate a 2D layer (Fig. 1c). Each
metallamacrocycle connects four adjacent metallamacrocycles
through pꢀ ꢀ ꢀp interactions. If the metallamacrocycles are
considered as nodes and the pꢀ ꢀ ꢀp interactions between the
two benzene rings are considered as linkers, then the 2D layer
possesses a (4, 4) net.
In complex 1, the flexible L1 ligand adopts a syn conformation
to coordinate the metal ions (Scheme 2a), providing a rectangular
metallamacrocycle. However, if the flexible ligand adopted an
anti conformation or a mixture of syn and anti conformations,
what kind of structure would result?
Fortunately, when we used other analogous ligands to
assemble with transition metal ions, compounds containing
an anti conformation or both syn and anti conformations of
the ligands were isolated.
1D ‘‘rainbow-like’’ zigzag chain (2). Single-crystal X-ray
diffraction measurements reveal that complex 2 crystallizes
in the monoclinic P21/c space group. The asymmetric unit of 2
Scheme 2 The syn and anti conformations of ligands 1–3.
c
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asymmetric unit possesses two crystallographically-independent
zinc ions (Zn1 and Zn2), one and a half L10 carboxylate
ligands, one m3-OH and one coordinated water molecule.
The half L10 ligand in the asymmetric unit lies about an
inversion centre. Zn1 is coordinated by three carboxyl oxygen
atoms and one bridging OHꢂ group in a tetrahedral geometry
with an average Zn–O distance of 1.935(7) A. Zn2 is
coordinated by two carboxyl oxygen atoms, one terminal
water molecule and two bridging OHꢂ groups in a triangle
bipyramidal geometry, giving an average Zn–O distance of
2.041(6) A.
Fig. 2 (a) The 1D ‘‘rainbow-like’’ chain of complex 2 along the a axis;
(b) the 2D supramolecular layer formed by pꢀ ꢀ ꢀp interactions between
chains.
Different from complexes 1 and 2 mentioned above, there
are two kinds of conformation of the L10 ligand in complex 3.
The two carboxylate groups of the syn-L10 ligand possess
different coordination modes: one adopts a bidentate bridging
mode to connect two zinc ions, while the other adopts a
monodentate coordination mode to link one zinc ion
(Scheme 2c). Both carboxylate groups of the anti-L10 ligand
adopt a bidentate bridging mode to link two zinc ions, as
shown in Scheme 2d. Thus, Zn1 and Zn2 are engaged by two
bridging OHꢂ groups and four carboxylate groups (two from
syn-L10 and two from anti-L10) to form a tetranuclear planar
SBU, Zn4(OH)2(CO2)4 (Fig. 4a) that is quite different from
the Zn4O(CO2)6 cluster14 but is similar to the reported
Cu4(OH)2(CO2)4 SBU.15 The tetranuclear SBUs are further
connected by anti-L10 along the b axis to generate a 1D
chain with the nearest Zn–Zn distance in different SBUs being
10.23 A.
consists of one zinc ion, one L9 ligand and one phen molecule.
The central zinc ion in 2 is six-coordinated by four oxygen
atoms from two different L9 ligands and two nitrogen atoms
from one chelating phen molecule. Both carboxylate groups of
L9 are deprotonated during the reaction and adopt a bidentate
chelating mode to chelate one zinc ion.
The L9 ligand adopts an anti conformation with dihedral
angles between the central benzene ring and the side benzene
rings of 59.5 and 69.51; the dihedral angle between the two side
benzene rings is 52.461. Thus, the whole ligand acts as a
bridging linker to connect zinc ions from opposite sides into
1D ‘‘rainbow-like’’ zig-zag chains (Fig. 2a), in which all the
zinc ions are in exactly a linear arrangement with the phen
molecules hanging in the same side of the line.
The strong pꢀ ꢀ ꢀp interactions between the coordinated phen
molecules in different chains further connects the 1D zig-zag
chains to form a 2D layer containing large 1D channels
(Fig. 2b). The dimensions of the 1D channels are 10.8 ꢁ 8.8 A,
in which the uncoordinated water molecules reside, as shown
in Fig. 3.
The syn- and anti-L10 ligands play different roles in
the formation of the 1D chain structure: the syn-L10 ligands
only connect zinc ions to form the tetranuclear SBU,
while the anti-L10 ligands not only take part in the formation
of the SBU, but also further link the SBU to form 1D
chains.
1D chain based on tetranuclear SBU (3). X-Ray diffraction
ꢀ
reveals that 3 crystallizes in the triclinic space group P1. The
Fig.
4 (a) The Zn4(OH)2(CO2)4 SBU in complex 3; (b) the
Fig. 3 (a) The 3D packing structure of complex 2 along the c axis
showing the uncoordinated water molecules locating in the 1D
channels.
syn-conformational L10 ligand in the SBU; (c) the 1D chain structure
formed by the anti-conformational L10 ligand (blue) connecting the
tetranuclear SBU.
c
2498 New J. Chem., 2010, 34, 2496–2501 This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2010

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Thermogravimetric analysis
Experimental
Synthesis of H2L1
Thermogravimetric analyses have been undertaken for complexes
1–3. A TGA study on an as-isolated crystalline sample of 1
showed a 17.74% weight loss from 50 to 300 1C, corresponding
to the loss of two coordinated dmf molecules (calc.: 17.8%).
The second gradual weight loss of 6.85% from 300 to 355 1C
Sodium methoxide (1.62 g, 30 mmol) was dissolved in absolute
methanol (200 mL) and cooled to room temperature.
2-Metcaptobenzoic acid (4.63 g, 30 mmol) was then added
with stirring, and the stirring was continued for 10 min. To the
resulting suspension was added 1,4-bis(bromomethyl)-2,3,5,6-
tetramethylbenzene (3.2 g, 10 mmol) and the reaction mixture
was stirred under reflux for 6 h. The solid was filtered while
still hot, dissolved in water and filtered to remove any
undissolved substance. The filtrate was acidified with dilute
hydrochloric acid, and the precipitates were filtered, washed
ꢂ
corresponded to the loss of one coordinated NO3 ion (calc.:
7.6%). After 355 1C, 1 started to decompose. For complex 2,
there was a slow weight loss of 9.92% from 50 to 170 1C,
in accordance with the loss of four uncoordinated water
molecules (calc.: 9.84%). After that, 2 started to decompose.
For complex 3, there was a slow weight loss of 5.89% from
100 to 155 1C, corresponding to the loss of one uncoordinated
EtOH molecule (calc.: 5.1%). The complex was stable up to
220 1C, after which it started to decompose.
1
with water and hot methanol. Yield: (2.09 g, 45%). H NMR
(300 MHz, DMSO-d6): d = 2.23 (s, 12 H), 4.66 (s, 4 H),
6.98–7.10 (m, 4 H), 7.18–7.23 (m, 4 H).
Synthesis of H2L9
Conclusion
H2L9 was prepared by a similar route to H2L1 using
1,4-bis(bromomethyl)benzene (2.64 g, 10 mmol) instead.
Yield: (2.46 g, 60%). 1H NMR (300 MHz, DMSO-d6):
d = 4.19 (s, 2 H), 7.2–7.9 (m, 4 H), 13.05(s, 1 H).
By employing 1,4-substituted flexible dicarboxylate ligands to
assemble with thulium ions and zinc ions, three metal–organic
supramolecules were constructed. In complex 1, the L1 ligand
adopts a syn conformation, which is the key to forming a 0D
metallamacrocycle. The anti conformation of the L9 ligand in
complex 2 results in the formation of a 1D ‘‘rainbow-like’’
chain structure. The mixed conformations (syn and anti) of the
L10 ligands play an important role in the formation of the
tetranuclear SBU and 1D chain in complex 3. Our research
further indicates that the conformation (syn and anti) of
the ligands has a significant effect on the structure of the
complexes (Scheme 3). The difference between the conformations
is that syn is convergent and anti is divergent, so the former
produces closed systems, while the latter leads to polymerisation.
The syn-L ligand is apt to generate zero-dimensional structures,
such as the metallamacrocycle in complex 1, while the anti-L
ligand is apt to forming extending frameworks, such as the 1D
chain structures in complexes 2 and 3. Further studies will
focus on the design and synthesis of novel frameworks by
controlling the conformation of the flexible carboxylate
ligands.
Synthesis of H2L10. A mixture of 1,4-bis(bromomethyl)-
2,3,5,6-tetramethylbenzene (3.2 g, 10 mmol), methyl salicylate
(3.08 g, 22.0 mmol) and K2CO3 (3.04 g, 22 mmol) in 40 mL
acetone was reflux for 6 h. The reaction mixture was filtered
while it was still hot, then cooled to room temperature and a
white precipitate formed. The white solid and an NaOH
aqueous solution (20 mL, 2 mol Lꢂ1) were mixed in 30 mL
of methanol and stirred for 8 h under reflux. After cooling to
room temperature, the clear solution was acidified to pH 2 by
diluted hydrochloric acid. The resulting white precipitate was
washed with water and dried in the air to give H2L10, yield:
(1.3 g, 30%). 1H NMR (300 MHz, DMSO-d6): d = 2.25
(s, 6 H), 5.14 (s, 2 H), 7.04 (t, 1 H), 7.38 (d, 1 H), 7.52 (m, 2 H),
12.50 (s, 1 H).
Preparation of Tm2(L1)2(dmf)4(NO3)2 (1)
Tm(NO3)2ꢀ6H2O (0.01 g), H2L1 (0.01 g, 0.0214 mmol) and
perchloric acid (01 d) in 1 mL mixed solvents of DMF, EtOH
and H2O (v/v = 5 : 2 : 1) were dissolved and heated in a sealed
tube at 90 1C for 2 d. Crystals of 1 were obtained (yield:
0.023 g, 65% based on H2L1). Elemental anal. calc. for 1: C,
45.71; H, 4.436; N, 4.998%; Found: C, 45.64; H, 4.641; N,
4.627%.
Preparation of [Zn(L9)(phen)]ꢀ4H2O (2)
Zn(NO3)2ꢀ6H2O (0.01 g, 0.034 mmol), H2L9 (0.01 g,
0.0243 mmol) and phen (0.01 g, 0.055 mmol) were dissolved
in a 10 mL mixture of DMF, EtOH and H2O (v/v = 5 : 2 : 1)
and heated in a sealed tube at 90 1C for 33 h. The resulting
colourless crystals were collected in 60% yield (0.01 g) on the
basis of H2L9. Elemental anal. calc. for 2: C, 56.54; H, 3.90; N,
3.88%; Found: C, 56.85; H, 4.08 N, 3.55%.
Preparation of [Zn4(L10)3(OH)2(H2O)2]ꢀ2H2Oꢀ2EtOH (3)
Zn(NO3)2ꢀ6H2O (0.01 g, 0.034 mmol), H2L10 (0.01 g,
Scheme 3 Schematic representations of metallamacrocycle, ‘‘rainbow’’
chain and 1D chain based on tetranuclear clusters.
0.023 mmol) and NEt3 (1 d) in a 10 mL mixture of DMF,
c
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EtOH and H2O (v/v = 5 : 2 : 1) was placed in a test tube at
room temperature. Colourless crystals of 3 suitable for X-ray
analysis were obtained at the bottom of the tube after a few
days (yield: 0.0149 g, 35% based on H2L10). Elemental anal.
calc. for 3: C, 56.24; H, 5.065%. Found: C, 55.59; H, 4.914%.
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Crystal data for 1: C64H76N6O18S4Tm2, M = 1683.41,
monoclinic, space group P21/n, a = 9.0709(7), b = 17.7102(13),
c = 21.7080(16) A, b = 100.6210(10), U = 3427.6(4) A3,
Z = 2, Dc = 1.631 Mg mꢂ3, m(Mo-Ka) = 0.71073 mmꢂ1
,
T = 298 K, 19 610 reflections collected. Refinement of 7659
reflections (488 parameters) with I > 2s(I) converged at final
R1 = 0.0339 (R1 all data = 0.0663), wR2 = 0.0730 (wR2 all
data = 0.0853), gof = 1.009.
Crystal data for 2: C34H28N2O6S2Zn,
M = 694.04,
monoclinic, space group P21/c, a = 7.8023(6), b = 31.614(2),
c = 15.2690(12) A, b = 103.204(2), U = 3666.7(5) A3, Z = 4,
Dc = 1.243 Mg mꢂ3, m(Mo-Ka) = 0.71073 mmꢂ1, T = 298 K,
15 623 reflections collected. Refinement of 5253 reflections
(426 parameters) with I > 2s(I) converged at final R1
0.0758 (R1 all data = 0.1088), wR2 = 0.2053 (wR2 all
=
data = 0.2316), gof = 1.031.
Crystal data for 3: C39H41O12Zn2, M = 832.46, triclinic,
ꢀ
space group P1, a = 12.2854(19), b = 13.199(2), c =
14.514(2) A, a = 66.739(2), b = 65.433(3), g = 63.684(2),
U = 1853.5(5) A3, Z = 2, Dc = 1.492 Mg mꢂ3, m(Mo-Ka) =
0.71073 mmꢂ1, T = 298 K, 11 030 reflections collected.
Refinement of 8032 reflections (498 parameters) with I >
2s(I) converged at final R1 = 0.00548 (R1 all data = 0.1180),
wR2 = 0.1036 (wR2 all data = 0.1293), gof = 0.988.
Acknowledgements
We gratefully acknowledge the financial support of the NSF of
China (Grant 90922014, 20701025), the NSF of Shandong
Province (Y2008B01, BS2009CL007), the 973 Program
(no. 2008CB617508) and Shandong University.
7 M. D. Allendorf, C. A. Bauer, R. K. Bhakta and R. J. T. Houk,
Chem. Soc. Rev., 2009, 38, 1330.
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