Construction and properties of six metal-organic frameworks based on the newly designed 2-(p-bromophenyl)-imidazole dicarboxylate ligand

Article abstract of DOI:10.1021/cg301570p

The newly designed organic ligand 2-(p-bromophenyl)-1H-imidazole-4,5- dicarboxylic acid (p-BrPhH₃IDC) has been successfully prepared and its coordination features were explored. By the reactions of p-BrPhH ₃IDC with main group or tra

Full text of DOI:10.1021/cg301570p

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Article
Construction and Properties of Six MOFs Based on the Newly
Designed 2-(p-Bromophenyl)-Imidazole Dicarboxylate Ligand
yu zhang, Beibei Guo, Li Li, Shaofeng LIu, and Gang Li
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg301570p • Publication Date (Web): 27 Nov 2012
Downloaded from http://pubs.acs.org on November 30, 2012
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Construction and Properties of Six MOFs Based on the Newly
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Designed 2-(p-Bromophenyl)-Imidazole Dicarboxylate Ligand
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Yu Zhang, Beibei Guo, Li Li, Shaofeng Liu, Gang Li*
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001,
Henan, P. R. China
ABSTRACT: The newly designed organic ligand, 2ꢀ(pꢀbromophenyl)ꢀ1Hꢀimidazoleꢀ4,5ꢀdicarboxylic acid
(pꢀBrPhH3IDC) has been successfully prepared and explored its coordination features. By the reactions of
pꢀBrPhH3IDC with main group or transition metals, six metalꢀorganic frameworks, namely,
[Ca(pꢀBrPhHIDC)(H2O)2]n (1), [Sr(pꢀBrPhHIDC)(H2O)]n (2), [Zn(pꢀBrPhHIDC)(H2O)]n (3),
{[Co(pꢀBrPhH2IDC)2]ꢁ2H2O}n
(4),
[Cd1.5(pꢀBrPhHIDC)(pꢀBrPhH2IDC)(H2O)]n
(5)
and
{[Cd2(pꢀBrPhHIDC)2(4,4′ꢀbipy)]⋅4H2O}n (4,4′ꢀbipy = 4,4′ꢀbipyridine) (6) have been synthesized under
hydro(solvo)thermal conditions. Xꢀray singleꢀcrystal analyses reveal that they have rich structural
chemistry ranging from oneꢀdimensional (1D) (3), twoꢀdimensional (2D) (1, 2, 4 and 5) to
threeꢀdimensional (3D) polymers (6). Furthermore, the existence of intermolecular hydrogen bonds and/or
π⋅⋅⋅π stacking interactions between the aromatic groups supplies the additional stabilization for the
solidꢀstate supramolecular structures of polymers 3, 4 and 5. The solidꢀstate photoluminescence properties
of the polymers 1ꢀ6 have been investigated as well.
INTRODUCTION
In the last two decades, more and more researchers pay attention to the construction of
various metalꢀorganic frameworks (MOFs)1 not only due to their multiple applications in gas
separation and storage,2 chemical and biological sensing,3 ion exchange,4 chirality,5
magnetism,6 catalysis7 and fluorescent materials 8
etc., but also for their intriguing
,
* To whom correspondence should be addressed. Eꢀmail: gangli@zzu.edu.cn. Fax: +86ꢀ371ꢀ67781764.
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architectures and fascinating topologies.9 Among them, zeroꢀdimensional (0D) multinuclear
complexes, oneꢀdimensional (1D) helical and zigzag chains, twoꢀdimensional (2D) grids,
threeꢀdimensional (3D) porous structures, interpenetrating networks have been presented.10
By previous reports, people found that many factors may seriously influence on the structures
of the resulting complexes, such as the multifunctional bridging ligands,11 kinds of metal salt,
the solvent system, pH value, the metalꢀtoꢀligand ratio, reaction temperature and time, and so
on.12 At all events, people spend the most time on the design and synthesis of the
multifunctional organic bridging ligands to get desired complexes. For example,
imidazoleꢀ4,5ꢀdicarboxylic acid (H3IDC) and its 2ꢀposition substituted derivatives have six
potential donor atoms: two imidazole nitrogen and four carboxylate oxygen atoms, which can
build up a large number of diverse architectures.13,14
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Recently, our group is interested in designing and preparing the H3IDC derivatives bearing
aromatic groups at the 2ꢀposition of imidazole ring, whose coordination features have been
explored by us. Some transition metal or main group metal MOFs from the six related
organic
ligands,
2ꢀphenylꢀ1Hꢀimidazoleꢀ4,5ꢀdicarboxylic
acid
(PhH3IDC),
(NH3IDC),
2ꢀ(2ꢀnaphthyl)ꢀ1Hꢀimidazoleꢀ4,5ꢀdicarboxylic
acid
acid
acid
2ꢀ(pꢀmethylphenyl)ꢀ1Hꢀimidazoleꢀ4,5ꢀdicarboxylic
2ꢀ(pꢀhydroxylphenyl)ꢀ1Hꢀimidazoleꢀ4,5ꢀdicarboxylic
2ꢀ(3,4ꢀdimethylphenyl)ꢀ1Hꢀimidazoleꢀ4,5ꢀdicarboxylic
(pꢀMePhH3IDC),
(pꢀOHPhH3IDC),
(DMPhH3IDC) and
acid
2ꢀpꢀmethoxyphenylꢀ1Hꢀimidazoleꢀ4,5ꢀdicarboxylic acid (MOPhH3IDC) have been
successfully prepared by our laboratory.15 In these MOFs, the imidazole dicarboxylate ligands
bearing bulky conjugate groups all indicate strong coordination abilities and diversity of
coordination modes. Prompted by these interesting findings, herein, we introduce the
electronꢀwithdrawing group, bromine to phenyl unit and obtain a new organic ligand
2ꢀ(pꢀbromophenyl)ꢀ1Hꢀimidazoleꢀ4,5ꢀdicarboxylic acid (pꢀBrPhH3IDC), and hope to
continuously explore its coordination characteristic from both theoretical and experimental
aspects.
In this contribution, we report the syntheses, architectures and characterization of six
coordination polymers, namely, [Ca(pꢀBrPhHIDC)(H2O)2]n (1), [Sr(pꢀBrPhHIDC)(H2O)]n (2),
[Zn(pꢀBrPhHIDC)(H2O)]n
(3),
{[Co(pꢀBrPhH2IDC)2]ꢁ2H2O}n
(4),
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[Cd1.5(pꢀBrPhHIDC)(pꢀBrPhH2IDC)(H2O)]n
(5)
and
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7
8
{[Cd2(pꢀBrPhHIDC)2(4,4′ꢀbipy)]⋅4H2O}n (4,4′ꢀbipy = 4,4′ꢀbipyridine) (6) (Scheme 1). The
structural studies reveal that both 1 and 2 are twoꢀdimensional (2D) grid structures containing
main group metals. The structures of polymers 3, 4, 5 and 6 are ranging from chain (1D) to
sheet (2D), and to interpenetrating network (3D). Moreover, the pꢀBrPhH3IDC ligand exhibits
abundant coordination modes (Scheme 2), which confirms the theoretical prediction. Finally,
the solidꢀstate photoluminescence properties of polymers 1-6 have been investigated at room
temperature as well.
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Scheme 1. Syntheses of Complexes 1-6
.
Ca(NO ) 4H O
3 2
2
H O NaOH 150OC 96 h
[Ca(pꢀBrPhHIDC)(H O) ]
1
2D
2D
2
2 n
2
Sr (NO )
3 2
HOOC
COOH
[Sr(pꢀBrPhHIDC)(H O)]
2
Et N 150OC 96 h
2
n
CH CN/H O
3
3
2
.
Zn(NO ) 6H O
N
NH
3 2
2
O
[Zn(pꢀBrPhHIDC)(H O)]
3
4
5
6
1D
2
n
160 C 72 h
Et N
3
CH OH/H O
3
2
+
.
Co (NO ) 6H O
3 2
2
.
160OC 72 h
{[Co(pꢀBrPhH IDC) ] 2H O}
2D
2D
2
2
2
n
CH OH/H O Et N
3
3
2
.
Cd(NO ) 4H O
3 2
2
[Cd (pꢀBrPhHIDC)(pꢀBrPhH IDC)(H O)]
n
1.5
2
2
Br
CH CN/H O
160OC 72 h
Et N
3
3
2
pꢀBrPhH3IDC
.
'
Cd(NO ) 4H O + 4,4 ꢀbipy
3 2
2
'
{[Cd (pꢀBrPhHIDC) (4,4 ꢀbipy)] 4H O}
¡¤
2
2
2
n
3D
O
Et N
3
CH CN/H O
160 C 72 h
3
2
Scheme 2. Coordination Modes of the p-BrPhH3IDC ligand
M
M
O
N
M
O
N
M
O
O
M
O
O
N
O
O
O
O
O
O
M
M
M
M
HN
N
M
HN
M
Br
Br
Br
c
a
b
M
O
N
O
N
O
N
O
N
OH
N
O
OH
OH
HN
M
O
O
O
M
O
O
HO
O
O
M
HN
M
N
M
M
M
M
Br
Br
Br
Br
g
e
d
f
3
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EXPERIMENTAL SECTION
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Materials. All chemicals are of reagent grade quality obtained from commercial sources
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and used without further purification. The organic ligand
according to literature procedure.16
pꢀBrPhH3IDC was prepared
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The C, H and N microanalyses were carried out on a FLASH EA 1112 analyzer. IR spectra
were recorded on a Nicolet NEXUS 470ꢀFTIR spectrophotometer as KBr pellets in the
400ꢀ4000 cmꢀ1 region. Fluorescence spectra were characterized at room temperature by an
Fꢀ4500 fluorescence spectrophotometer. The optimized geometry and natural bond orbital
(NBO) charge distribution of the free ligand pꢀBrPhH3IDC were given by the GAUSSIAN 03
suite of programs. And all calculations were carried out at the B3LYP/6ꢀ311++G (d, p) level
of theory.17
Preparation of [Ca(p-BrPhHIDC)(H2O)2]n (1). A mixture of Ca(NO3)2⋅4H2O (11.8 mg,
0.05 mmol), ꢀBrPhH3IDC (15.6 mg, 0.05 mmol), and H2O (7 mL), NaOH (40 mg, 0.5 mmol)
p
were sealed in 25 mL Teflonꢀlined bomb and heated at 150 °C for 96 h. The reaction mixture
was then allowed to cool to room temperature at a rate of 10 °C/h. Colorless flakeꢀshaped
crystals of 1 were collected, washed with distilled water, and dried in air (65% yield based on
Ca). Anal. Calcd for C11H9BrN2O6Ca: C, 34.27; H, 1.82; N, 7.27%. Found: C, 34.50; H, 1.73;
N, 7.42%. IR (cmꢀ1, KBr): 3630 (s), 3419 (w), 3261 (s), 1894 (w), 1572 (w), 1557 (w), 1477
(m), 1396 (m), 1279 (s), 1226 (w), 1115 (m), 1010 (s), 863 (m), 813 (m), 723 (w), 682 (w),
588 (m), 490 (w).
Preparation of [Sr(p-BrPhHIDC)(H2O)]n (2). A mixture of Sr(NO3)2 (10.6 mg, 0.05
mmol), ꢀBrPhH3IDC (15.6 mg, 0.05 mmol), and CH3CN/H2O (3/4, 7 mL), Et3N (0.056 mL,
p
0.4 mmol) were sealed in 25 mL Teflonꢀlined bomb and heated at 150 °C for 96 h. The
reaction mixture was then allowed to cool to room temperature at a rate of 10 °C/h. Good
quality colorless acicular crystals of 2 were collected, washed with distilled water, and dried
in air (72% yield based on Sr). Anal. Calcd for C11H7BrN2O5Sr: C, 31.83; H, 1.69; N, 6.75%.
Found: C, 32.07; H, 1.92; N, 6.58%. IR (cmꢀ1, KBr): 3641 (m), 3426 (m), 3205 (m), 2922 (w),
1585 (s), 1566 (m), 1440 (s), 1468 (m), 1264 (m), 1109 (s), 855 (w), 834 (m), 811 (s), 729 (s),
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669 (w), 518 (m), 435 (w).
Preparation of [Zn(
0.05 mmol),
p
-BrPhHIDC)(H2O)]n (3). A mixture of Zn(NO3)2⋅4H2O (14.9 mg,
p
ꢀBrPhH3IDC (15.6 mg, 0.05 mmol), Et3N (0.056 mL, 0.4 mmol) and
9
CH3OH/H2O (3/4, 7 mL) were sealed in 25 mL Teflonꢀlined bomb and heated at 150 °C for
96 h. The reaction mixture was then allowed to cool to room temperature at a rate of 10 °C/h.
Colorless blockꢀshaped crystals of 3 were collected, washed with distilled water, and dried in
air (52% yield based on Zn). Anal. Calcd for C11H7BrN2O5Zn: C, 33.63; H, 1.78; N, 7.13%.
Found: C, 33.33; H, 1.49; N, 7.46%. IR (cmꢀ1, KBr): 3384 (m), 3243 (m), 1716 (w), 1651 (s),
1476 (m), 1425 (w), 1280 (s), 1128 (m), 937 (m), 828 (s), 733( s), 693 (w), 551 (m).
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Preparation of {[Co(p-BrPhH2IDC)2]·2H2O}n (4). A mixture of pꢀBrPhH3IDC (15.6 mg,
0.05 mmol), Co(NO3)2ꢁ6H2O (14.6 mg, 0.05 mmol), Et3N (0.056 mL, 0.4 mmol), and
CH3OH/H2O (3/4, 7 mL) were sealed in 25 mL Teflonꢀlined autoclave and heated for 72 h at
160 °C under autogenous pressure. Then the reaction mixture was allowed to cool to room
temperature at a rate of 10 °C/h. Red cubicꢀshape crystals of 4 were collected in 51% yield
(based on Co), washed with distilled water and dried in air. Anal. Calcd for
C22H16Br2N4O10Co: C, 36.92; H, 2.24; N, 7.83%. Found: C, 36.58; H, 2.48; N, 7.57%. IR
(cmꢀ1, KBr): 3584 (w), 3371 (m), 1915 (w), 1558(w), 1428 (w), 1394 (w), 1360 (w), 1285
(m), 1259 (m), 1123 (s), 1070 (s), 1001 (s), 878 (w), 836 (s), 799 (w), 750 (m), 676 (w), 496
(w).
Preparation of [Cd1.5(
p
-BrPhHIDC)(p-BrPhH2IDC)(H2O)]n (5). A mixture of
Cd(NO3)2 4H2O (14.6 mg, 0.05 mmol),
⋅
p
ꢀBrPhH3IDC (15.6 mg, 0.05 mmol), Et3N (0.056 mL,
0.4 mmol) and CH3CN/H2O (3/4, 7 mL) were sealed in 25 mL Teflonꢀlined bomb and heated
at 160 °C for 72 h. The reaction mixture was then allowed to cool to room temperature at a
rate of 10 °C/h. Colorless clubꢀshaped crystals of 5 were collected, washed with distilled
water, and dried in air (68% yield based on Cd). Anal. Calcd for C22H13BrN4O9Cd1.5: C, 32.76;
H, 1.61; N, 6.95%. Found: C, 33.01; H, 1.88; N, 6.67%. IR (cmꢀ1, KBr): 3605 (m), 3428 (w),
1714 (m), 1480 (w), 1402 (w), 1123 (s), 1012 (s), 978 (w), 855(w), 834 (s), 777 (m), 735 (s),
565 (m).
Preparation of {[Cd2(
p
-BrPhHIDC)2(4,4
′
-bipy)]
⋅
4H2O}n (6).
A
mixture of
Cd(NO3)2 4H2O (14.6 mg, 0.05 mmol),
⋅
p
ꢀBrPhH3IDC (15.6 mg, 0.05 mmol), Et3N (0.056 mL,
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0.4 mmol), 4,4
′ꢀbipy (7.8 mg, 0.05 mmol) and CH3CN/H2O (3/4, 7 mL) were sealed in 25 mL
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7
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Teflonꢀlined bomb, which was heated to 160 °C for 72 h. And then cooled to room
temperature at a rate of 10 °C/h. Good quality colorless crystals for 6 were filtered off,
washed with distilled water and dried in air (77% yield based on Cd). Anal. Calcd. for
C32H26Br2N6O12Cd2: C, 35.85; H, 2.43; N, 7.84%. Found: C, 35.57; H, 2.21; N, 7.65%. IR
(cmꢀ1, KBr): 3418 (w), 3051 (w), 1688 (m), 1559 (w), 1384 (w), 1324 (w), 1257 (m), 1117
(w), 1069 (m), 1000 (s), 960 (w), 853 (s), 838 (s), 809 (s), 784 (m), 717 (w), 628 (s), 555 (w),
487 (w), 468 (s).
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Crystal Structure Determinations. Crystal data and experimental details for the
compounds 1ꢀ6 are contained in Table 1. Measurements of 1ꢀ6 were made on a Bruker smart
APEXII CCD diffractometer with a graphiteꢀmonochromated Moꢀ
Å). Single crystals of 1ꢀ6 were selected and mounted on a glass fiber. All data were collected
at room temperature using the ꢀ2 scan technique and corrected for Lorenzꢀpolarization
Kα radiation (λ = 0.71073
ω
θ
effects. A correction for secondary extinction was applied.
The six structures were solved by direct methods and expanded using the Fourier
technique. The nonꢀhydrogen atoms were refined with anisotropic thermal parameters.
Hydrogen atoms were included but not refined. All calculations were performed using the
SHELXꢀ97 crystallographic software package.18 Selected bond lengths and angles, and the
parameters of hydrogen bonds for 1ꢀ6 are listed in Tables S1 and S2, respectively (Supporting
Information). CCDC 906073ꢀ906078 contain the supplementary crystallographic data for 1ꢀ6,
respectively. These data can be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam. ac.uk/data_request/cif.
RESULTS AND DISCUSSION
Geometry of the Free Ligand and Synthesis. Recently, we have investigated the phenyl
substituent effect of PhH3IDC ligand.15a And subsequently the substituent effect of the
p
ꢀmethylphenyl, pꢀhydroxylphenyl, 3,4ꢀdimethylphenyl and pꢀmethoxyphenyl in the related
imidazole dicarboxylate ligands have been calculated by quantum chemical method, and
confirmed by experimental results. The results indicate that as these electronꢀdonor substituted
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groups, ꢀCH3, ꢀOH, ꢀOCH3, were introduced into the phenyl group of the PhH3IDC system, the
negative NBO charges mainly distribute on the oxygen and nitrogen atoms and most of them
are increase in comparison with the free ligand H3PhIDC. Furthermore, we hope to
continuously explore the substituent effect of electronꢀwithdrawing groups in the PhH3IDC
system, and study their coordination features.
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Herein, we firstly probe
theoretical calculation. The optimized geometry and NBO charge distributions of the free
ligand
ꢀBrPhH3IDC have been calculated by the B3LYP/6ꢀ311++G(d, p) level.17 The
computed results (Scheme 3) display that the free ligand ꢀBrPhH3IDC has two characteristics:
pꢀbromophenyl substituent effect on the pꢀBrPhH3IDC ligand by
p
p
(1) The negative NBO charge distribution values for the electron donors, N and O, are kindred
with the corresponding atoms and the potential outstanding coordination ability of
p
ꢀBrPhH3IDC exits in theory (ꢀ0.664, ꢀ0.645, ꢀ0.635, and ꢀ0.597 for four carboxylate oxygen
atoms, ꢀ0.497 and ꢀ0.456 for two imidazole nitrogen atoms). (2) As shown in Scheme 3,
compared with the free ligand PhH3IDC, the introduction of 2ꢀ ꢀbromine atom into
ꢀMePhH3IDC has a slight effect on the NBO charge distributions of oxygen and nitrogen
atoms. The negative NBO charge distributions on one imidazole nitrogen and one carboxylate
oxygen atoms of ꢀBrPhH3IDC are slightly increased, and on the other N and O atoms are
slightly decreased. However, the calculation results still show that the oxygen and nitrogen
atoms of the ꢀBrPhH3IDC ligand have the potential ability of coordination to metal ions, and
can be confirmed by our present experimental results. At the same time the imidazoleꢀ and
two COOꢀ units can be deprotonated in the six polymers herein, also leading to the
deprotonated
ꢀBrPhH3ꢀnIDCnꢀ (n = 1 or 2) anions. As shown in Scheme 2, the ligand
ꢀBrPhH3IDC shows various coordination modes. To understand the coordination modes of
ꢀBrPhH3IDC, we have analyzed the the Cambridge Structure Database, and found about
p
p
p
p
,
H
H
p
p
p
more than four hundred complexes bearing H3IDC and its 2ꢀposition substituted derivatives in
the Database. Through comparison the similarities and differences of the coordination modes
about the imidazole dicarboxylate ligands in CCDC, we found that each coordination mode of
p
ꢀBrPhH3IDC can be found in previous different imidazole dicarboxylateꢀbased complexes.15e
This suggests that no matter the derivatives of H3IDC contain what kinds of 2ꢀposition
substituent: electronꢀwithdrawing or electronꢀdonor groups, they all show diversity of
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coordination modes.
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In experimental process, we adopted the ligand pꢀBrPhH3IDC to react with main group or
transition metal ions, respectively, and found that the ligand shows various coordination
modes (Scheme 2). Consequently, polymers 1 and 2 based on IIA group present
twoꢀdimensional sheets and the transitionꢀmetal polymers 3ꢀ6 possess oneꢀdimensional,
twoꢀdimensional or threeꢀdimensional structures.
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Because Ca(II) and Sr(II) ions are residing the same main group, the similar structural
complexes 1 and 2 can be obtained. It is noteworthy that the stoichiometry of the starting
materials and introduction of coligands are two important factors for the formations of
polymers 1ꢀ6. Crystals of 1ꢀ6 can be successfully produced in the metalꢀtoꢀligand mole ratio
of 1:1, while other stoichiometry has given products with a very low yield. When we
introduced 4,4′ꢀbipy acting as coligand to participate in the coordination to the metal Cd(II)
ion, an interesting threeꢀdimensional Cd(II) polymer 6 can be obtained, which is different
from polymer 5. Obviously, the auxiliary ligand has a significant influence on the structural
formation of 6.
Scheme 3. The Optimized Geometries and NBO Charge Distributions Of the Free Ligands PhH3IDC
And p-BrPhH3IDCa
PhH3IDC
p-BrPhH3IDC
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a The blue ball represents N atoms, the red ball represents O atoms, the gray ball represents C atoms and
the reddish brown ball represents Br atom.
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The pH values of the solution before and after reaction are ca. 8 and 6, respectively, during
the reactions. The reaction of metal salts with the pꢀBrPhH3IDC ligand, Et3N or NaOH,
CH3CN/H2O or CH3OH/H2O under hydro(solvo)thermal conditions successfully gave six
polymers. Moreover, the polymers 1 and 2 under 150 °C for 96 h are obtained, while the
polymers 3 to 6 can be got under 160 °C for 72 h. Summarily, through eminent synthetic
conditions, such as metal/ligand molar ratio, solvent, pH values, temperature, etc., a series of
charming coordination complexes are received. It is believed that more metal complexes with
interesting structures as well as physical properties will be synthesized from this kind of
ligand, and our laboratory is going on this work.
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Crystal Structures of Crystalline Polymers [Ca(
p-BrPhHIDC)(H2O)2]n (1) and
[Sr( -BrPhHIDC)(H2O)]n (2). A pair of polymers 1 and 2 is obtained by the reactions of
p
pꢀBrPhH3IDC ligand with two kinds of metal ions within the same group, Ca and Sr,
respectively, which show 2D layers.
In polymer 1, the central Ca(II) cation is surrounded entirely by eight oxygen atoms (Figure
S1), in which two oxygen atoms (O5, O6) are from two coordination water molecules, O1a
and O3a from one carboxylatoꢀchelating p-BrPhHIDC2ꢀ anion, O1 and O2 from one
bidentateꢀchelating carboxylato groups of another p-BrPhHIDC2ꢀ anion, and another two
monodentate oxygen atoms (O4c and O2b ) from two distinct organic ligands. The CaꢀO
bonds are in the range of 2.382(2) to 2.714(2) Å (average CaꢀO distance being 2.465 Å),
which is close to the reported 8ꢀcoordinated Ca(II) polymers, [Ca(2,5ꢀPDC)(DMF)]n,
19d
[Ca(2,4ꢀPDC)(H2O)]n and [Ca(2,4ꢀPDC)(DMF)]n
(PDC = Pyridinedicarboxylic acid;
average CaꢀO distance being 2.46 (±0.08) Å), and also consistent with the related imidazole
19h
dicarboxylate 8ꢀcoordinated pyridineꢀdicarboxylic acid {[Ca2(EIDC)2(H2O)2]ꢁH2O}n
(EH3DIC = 2ꢀethylꢀ1Hꢀimidazoleꢀ4,5ꢀdicarboxylic acid; average CaꢀO distance being 2.428
Å). The bond angles around the Ca(II) ion vary from 49.68(7) to 163.66(7)°, which are
comparable to those previous Ca(II) complexes.19
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In polymer 1, the pꢀBrPhHIDC2ꢀ ligand presents
coordination mode (Scheme 2a). The
4ꢀpꢀBrPhHIDC2ꢀ ligand bridges neighboring Ca(II)
ꢀ4ꢀkO: kO′, O′′: kO′′, O′′′: kO′′′
ꢀ
6
ions to form a 1D chain along the cꢀdirection. The pꢀBrPhHIDC2ꢀ ligands further link the
adjacent infinite chains to get a 2D layer (Fig. 1). Furthermore, the layers connected by
weak intermolecular πꢀπ stacking interactions give rise to a 3D metallosupramolecular
architecture (Figure S2), and the hydrogen bonding N–H…O and O–H…O interactions
further stabilize the supramolecular network. The detailed hydrogen bond parameters are
listed in Table S2 (Supporting Information).
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1D chain
Figure 1. The sheet structure of 1 (H atoms omitted for clarity).
In polymer 2, the central Sr(II) atom is ligated by nine oxygen atoms (Figure S3), which
are from one coordinated water molecule (O3) and five individual pꢀBrPhHIDC2ꢀ ligands (O1,
O2; O1a, O5a; O5d, O6d; O2b and O6c). The Sr–O bond distances vary from 2.484(3) to
2.754(3) Å, which are longer than the Ca–O bond length. The bond angles of O–Sr–O range
from 47.34(7) to 176.73(8)°. Each pꢀBrPhHIDC2ꢀ anion adopts the same coordination
mode,15h
ꢀ5ꢀkO: kO, O′: kO′,O′′: kO′′, O′′′: kO′′′ (Scheme 2b). As illustrated in Figure 2, six
Sr(II) atoms form a distorted hexagonal ring, and the distance of neighboring Sr…Sr are
3.9916(4) Å and 4.4632(5) Å, respectively. Similar to the Ca(II) atoms of polymer 1, the Sr(II)
atoms are connected through the carboxylate oxygen atoms to shape countless
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corrugatedꢀshape chains. These adjacent chains are further linked by the O atoms from the
carboxyl groups leading to a spectacular 2D grid.
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Both the central metal ions of polymers 1 and 2 are surrounded only by oxygen atoms,
however, as mentioned above, the Sr−O distances are longer than Ca−O distances, which is
obvious due to the Sr(II) atom radius being larger than that of Ca(II) atom.
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By searching the literatures, we found that the Sr(II) polymers bearing the related imidazole
dicarboxylate ligands are limited. Only one 3D {[Sr(ꢀ2ꢀPhH2IDC)2(H2O)4]}n13g, three 2D
15k
[Sr(EH2IDC)2(H2O)2]n15e, [Sr(PhHIDC)(H2O)]n and [Sr(pꢀMePhHIDC)(H2O)]n
polymers
have been reported. The successful preparation of the polymer 2 herein gives us more chance
to study the structures and properties of the related polymers.
Figure 2. The layer structure of 2 containing hexagonal rings (C, N, and H atoms omitted for clarity).
Crystal Structure of Crystalline Polymer [Zn(p-BrPhHIDC)(H2O)]n (3). According to
Xꢀray analysis, polymer 3 is an infinite 1D chain. Clearly, each pꢀBrPhHIDC2ꢀ ligand adopts
the coordination mode,
ꢀ2ꢀkN, O: kN′, O′ (Scheme 2c). The central Zn(II) ion is
fiveꢀcoordinated by two carboxylate oxygen atoms (O1 and O1a), two nitrogen atoms (N1
and N1a) from two individual pꢀBrPhHIDC2ꢀ ligands, and O3 from the coordinated water
(Figure S4). The Zn–N (N1 and N1a) distance is 2.104(4) Å and the Zn−O (O1 and O1a)
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bond length is 2.069(4) Å, which is slightly longer than Zn−O3 distance (2.021(7) Å).
Additionally, the bond angles around Zn(II) ion vary from 82.03(16) to 172.6(3)°. The
addison parameter value (τ = 0.875) of fiveꢀcoordinated Zn atom shows that the geometry
around the Zn(II) atom is distorted trigonal bipyramidal geometry.20
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It is worth noting that the nitrogen atoms from pꢀBrPhHIDC2ꢀ ions link neighboring Zn(II)
ions to build up a 1D chain along the cꢁaxis as shown in Fig. 3a, and the intrachain
neighboring Zn…Zn distance is 6.4488(3) Å.
The intermolecular hydrogen bonds join the infinite parallel chains to construct many
layers. The crystal structure 3 contains two kinds of hydrogen bonds O3ꢀH3⋅⋅⋅Br1a and
O3ꢀH3⋅⋅⋅O2b. Obviously, all of the donor oxygen atoms are from the coordinated water
molecules, but the acceptor atoms are Br and O from pꢀBrPhHIDC2ꢀ ligands. What’s more, the
O3ꢀH3…Br1a bonds increase the stability of the solidꢀstate architecture. Finally, the 3D
supramolecular structure is assembled by the weak πꢀπ stacking interactions, the distance
between two neighboring phenyl rings and imidazole rings of pꢀBrPhHIDC2ꢀ anion is
8.1974(3) Å (Figure 3b).
(a)
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Figure 3. (a) View of the 1D chain of 3 (H atoms omitted for clarity). (b) Crystal packing diagram of 3
showing the stacking between the adjacent chains (Part of H atoms omitted for clarity).
πꢀπ
Crystal Structure of Crystalline Polymer {[Co(p-BrPhH2IDC)2](H2O)2}n (4). The
result of singleꢀcrystal Xꢀray diffraction analysis indicates that polymer 4 indicates a 2D
framework.
As shown in Figure S5, the central Co(II) ion is in a sixꢀcoordinated environment, which
is completed by four O atoms (O2, O2c, O3a and O3b) and two N atoms (N1 and N1c) from
four individual pꢀBrPhH2IDCꢀ anions. The oxygen atoms (O2, O2c, O3a and O3b) constitute
the equatorial plane, with the LꢀCoꢀL (L=O or N) angles in the range of 78.67(6) – 180.00(7)°.
The two nitrogen atoms (N1 and N1c) occupy the axial positions. The Co–O bond lengths
vary from 2.0717(14) to 2.1285(14) Å, and the CoꢀN bond length is 2.1269(15) Å, which are
in the normal values and close to those observed for carboxylateꢀbased cobalt (II)
complexes.15f,21
All the pꢀBrPhH2IDCꢀ ligand in polymer 4 adopt the same coordination mode,
ꢀ2ꢀk N, O:
k O′ (Scheme 2d), and bridge Co(II) ions to form 1D helical chains: rightꢀhanded and
leftꢀhanded helical chains (Figure 4a). And then the adjacent helical chains are held together
by the pꢀBrPhH2IDCꢀ ligands forming a 2D framework (Figure 4b). Moreover, the four
ꢀ
2ꢀBrPhH2IDCꢀ anions join the four Co(II) ions to construct a rhombic grid. Within the grid,
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the distance of the CoꢀCo is 8.4984(9) Å (Figure 4b). Furthermore, the weak π–π interactions
between phenyl and imidazole rings (the dihedral angle of two adjacent benzene rings is
0.000(77)°, and the distance between the benzene rings are 8.1974(3) Å) can be observed.
Finally, the hydrogen bonds of N–H …O (N2ꢀH2...O5 2.812 Å, 175° and OꢀH⋅⋅⋅O
(O4ꢀH1⋅⋅⋅O1 2.456 Å, 178°) link these layers to generate an extended 3D supramolecular
network (Figure 4c).
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(a)
(b)
(c)
Figure 4. (a) The 1D rightꢀhanded helical and 1D leftꢀhanded helical chains. (b) The 2D sheet
comprising the infinite helical chains. (c) Crystal packing diagram of 4 showing intermolecular Hꢀbonds
and the
πꢀπ
stacking between the helical chains (Partial H atoms omitted for clarity).
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Crystal
Structures
of
Crystalline
(5)
Polymers
and
[Cd1.5(p-BrPhHIDC)(p-BrPhH2IDC)(H2O)]n
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{[Cd2(p-BrPhHIDC)2(4,4′-bipy)]⋅4H2O}n (6). Both polymers 5 and 6 are obtained through
the similar reactions of cadmium with the imidazole dicarboxylate ligand. The
hydro(solvo)thermal reaction conditions of polymers 5 and 6 are same, such as pH value,
metal/ligand molar ratio, solvent, reaction temperature and time. The only difference lies in
the addition of 4,4′ꢀbipy in the synthesis of polymer 6, which caused the structural difference
of complexes 5 (2D sheet) and 6 (3D network).
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As depicted in Figure S6, the crystal unit of 5 contains two crystallographically
independent Cd(II) ions, one pꢀBrPhH2IDC2ꢀ anion and two coordinated H2O molecules.
Both Cd1 and Cd2 are sixꢀcoordinated and display a distorted octahedron [CdN2O4].
Additionally, the Cd1 and Cd2 are connected by two oxygen atoms from a carboxylate. The
Cd1 atom is surrounded by O1 and N, O1a and N1a from two chelating pꢀBrPhH2IDC2ꢀ
ligands, another two O6 and O6a atoms from two individual pꢀBrPhH2IDC2ꢀ anions. While
the Cd2 ion is chelated by two N donors (N3 and N2b) from different imidazole rings and
three carboxylato oxygen atoms (O4b, O4c and O5). The Cd–N and Cd–O bond distances
range from 2.238(3) to 2.314(3) Å and from 2.296(2) to 2.511(2) Å, respectively, and the
trans LꢀCdꢀL bond angles vary from 69.79(9) to 180.00(14)°, all of which are comparable to
those reported imidazole dicarboxylate Cd(II) complexes.22
The ligand pꢀBrPhH3IDC in polymer 5 can be singly deprotonated or doubly
deprotonated forming pꢀBrPhH3ꢀnIDCnꢀ (n = 1 or 2) anions, which shows two kinds of
coordinated modes, namely, ꢀ2ꢀ kN, O: kN′, O′ (Scheme 2e) and ꢀ3ꢀKN, O: kN′, O′: kO′′
(Scheme 2f), respectively. The pꢀBrPhHIDC2ꢀ and pꢀBrPhH2IDCꢀ units link Cd1 and Cd2
atoms to form an interesting 1D chain. As shown in Figure 5a, by the linkages of the
imidazole dicarboxylate ligands, the dinuclear Cd(II) cores and singleꢀnuclear Cd(II) atoms
are staggered linking. Notably, the 2D grid is composed by these chains bridged by
ꢀ
3ꢀBrPhHIDC2ꢀ anions (Figure 5b), in which there are two kinds of rhombus grids with
dimensions of 6.6890 Å × 5.3959 Å, and 5.3959 Å × 8.8562 Å, respectively. Furthermore, the
adjacent layers are stacked together through interlayer hydrogen bonds, resulting in a 3D
supramolecular solidꢀstate structure (Figure 5c), with the hydrogen bond distances of 2.480(4)
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ꢀ 2.926(4) Å.
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Xꢀray diffraction analysis reveals that complex 6 is a 3D framework. The asymmetric unit
of 6 is composed of two Cd(II) ions, two pꢀBrPhHIDC2ꢀ anions, one 4,4′ꢀbipy unit, and four
water molecules. As shown in Figure S7, the central Cd(II) ion is located in sixꢀcoordinated
environment and shows a distorted octahedral geometry, which is completed by three oxygen
atoms and two nitrogen atoms (O4b; O1a, N1a; O4 and N1) from three individual
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ꢀ
2-pꢀBrPhHIDC2ꢀ ligands, and another one nitrogen atom from the 4,4′ꢀbipy unit. The Co–O
bond lengths are in the range of 2.284(2)
to 2.333(3) Å.
–2.456(3) Å and those of Co–N vary from 2.275(3)
Compared with the polymer 5, the imidazole dicarboxylate ligand in polymer 6 adopts a
new coordination mode, 2ꢀkN, O: kN′, O′ (Scheme 2g), which may be due to the emergence
of 4,4′ꢀbipy. It is worth noting that two nitrogen atoms (N1, N2) from
2-BrPhHIDC2ꢀ anion
ꢀ
ꢀ
bridge neighboring Cd(II) ions to form a 1D helical chain as shown in Figure 6a. Moreover,
eight cadmium atoms compose a quadrangle [Cd8(pꢀBrPhHIDC)12(4,4′ꢀbipy)6], the
quadrangle are also connected by
chains are linked to a 2D grid by nitrogen atoms from bridging imidazole ring (Figure 6b). It
is noteworthy that the 2ꢀ4,4′ꢀbipy can pass through the adjacent layers to hold the layers into
ꢀ
2-pꢀBrPhHIDC2ꢀ ligands. Furthermore, the 1D infinite
ꢀ
an interpenetrating 3D framework (Figure 6c). To understand the complicated crystal
structure, topological analysis of network is used by the OLEX program. In polymer 6, the
Cd(II) can be viewed as 6ꢀconnected nodes which are connected to three
one 2ꢀ4,4′ꢀbipy ligands. Hence, the 3D network of 6 can be described as a 6ꢀconnected
topology with a point symbol of 3(6).6(6).7(3) 3.3.3.3.3.3.6.6.6.6.6.6.
ꢀ2-BrPhHIDC and
ꢀ
Comparing 5 with 6, the bridging 4,4′ꢀbipy group is quite important in forming the 3D
structure. Obviously, the employment of the bridging ligands with Nꢀdonors would enrich the
kinds of complexes.23 Also, the Nꢀcontaining bridging coligands such as 4,4′ꢀbipy, piperazine
and so on, usually favor the construction of the 3D structures.15d,24
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(b)
(c)
Figure 5. (a) The 1D chain of polymer 5 built by the imidazole dicarboxylate ligands and Cd(II) ions. (H
atoms omitted for clarity). (b) View of the 2D layer in 5 (partial organic ligands omitted for clarity). (c)
The 3D supramolecular network of 5 supported by intermolecular hydrogen bonds.
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(c)
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Figure 6. (a) The infinite chain of 6 built by pꢀBrPhHIDC2ꢀanions and metal ions. (b) View of the 2D sheet
for 6 (4,4’ꢀbipy and partial imidazole dicarboxylate ligands omitted for clarity). (c) The 3D framework of 6
(partly atoms omitted for clarity). (d) Schematic representation of the 6ꢀconnected topology.
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Infrared Spectra, Thermal Analyses and Luminescent Properties. The IR spectra
display characteristic absorption bands for water molecules, carboxylate, imidazole and
phenyl units. Compounds 1ꢀ6 show broad absorption bands in the range of 3400–3650 cmꢀ1,
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which indicates the presence of νN–H and the νO–H stretching frequencies of imidazole rings
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and coordinated water molecules, respectively. Six complexes exhibit strong characteristic
absorptions around the frequency range 1557−1570 cm νas(COOꢀ) and 1450−1485 cm
νs(COOꢀ), respectively. The characteristic IR band of the phenyl ring at 840–860 cmꢀ1 due to
δ=C–H vibrations.
In order to characterize the stabilities of the frameworks, thermal gravimetric analyses
(TGA) of 1-6 were carried out in air atmosphere (Figure 7).
For complex 1, the first weight losses corresponds to the removal of two coordinated water
molecules before 215.8 °C (observed 8.11%, calculated 9.34%). The second to fourth weight
loss steps are from 215.8 to 985.0 °C. The total weight loss of the three steps is 76.64%
(calculated 76.12%), which corresponds to the decomposition of the pꢀBrPhHIDC2ꢀ ligands.
The remaining weight of 15.25% corresponds to the percentage (calculated 14.54%) of Ca
and O components, indicating that the final product is CaO.
For polymer 2, it is stable up to 224.3 °C, and then reveals a weight loss of 4.34%
(calculated 4.31%) from 224.3 to 396.5 °C for the removal of one coordination water
molecule. When the temperature is higher than 396.5 °C, decomposition of the pꢀBrPhHIDC2ꢀ
(observed 69.87%, calculated 70.71%) can be observed. A white amorphous residue is SrO
(observed 25.79%, calculated 24.98%).
The thermal analysis curve indicates that polymer 3 exhibits a threeꢀstage decomposition
process. The first weight loss of 17.64% observed from 280.1 to 393.1 °C, which corresponds
to a loss of one coordinated water molecule and parts of organic ligand. When the
temperature is higher than 393.1°C, the other organic units are removed (observed 42.61%).
The remaining weight of 19.75% (calculated 20.63%) is close to the percentage of the Zn and
O components, indicating that the final residue is ZnO.
The TG analysis of 4 revealed that the first and second weight loss of 16.58% is between
95.0 and 289.1 °C (calculated 17.34%), corresponding to losses of two free water molecules
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and two
ꢀ
ꢁCOOꢀ units. It keeps losing weight from 289.1 to 596.2 °C (observed 70.27%,
calculated 71.05%), which can be attributed to the loss of the remaining pꢀBrPhHIDC2ꢀ ligand,
respectively. The remaining weight of 12.15% (calculated 11.61%) is close to the percentage
of the Co and O components, indicating that the final gray product is 0.5Co2O3.
For polymer 5, it firstly loses the coordinated water molecule in the temperature range of
172.7 to 314.5 °C (observed 2.86%, calculated 2.23%). It keeps losing weight from 314.5 to
713.7 °C, corresponding to the decomposition of two pꢀBrPhHIDC2ꢀ units. After the
temperature of 713.7 °C, a plateau region is observed. The final residue is 1.5CdO (observed
22.34%, calculated 23.90%).
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The TGA curve of polymer 6 shows that the first weight loss of 6.56% (calculated 6.72%)
occurs at about 94.2°C, which is attributed to the loss of four free water molecules. The
second weight loss of 16.28% between 285.9 and 342.3 °C corresponds to lose of one
4,4′ꢀbipy molecule and one
ꢀ
ꢁCOOꢀ per formula unit from the crystal lattice (calculated
18.67%). Subsequently, it keeps losing weight beyond the temperature of 342.3 °C, which is
attributed to the loss of the remaining pꢀBrPhHIDC2ꢀ ligands (observed 50.91%, calculated
50.64%). The brown amorphous residue is 2CdO (observed 24.25%, calculated 23.97%).
Figure 7. The TG curves for complexes 1-6.
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Considering coordination complexes with d10 metal ions usually indicating relatively strong
luminescence, the solidꢀstate photoluminescence properties of complexes 1-6 and the
corresponding free pꢀBrPhH3IDC ligand have been investigated at room temperature (Figure
8). The free pꢀBrPhH3IDC ligand displays very weak luminescence, almost no emission,
which is attributed to the quenching effect of the bromine ion (Figure S8). Emission bands are
observed at 355 nm (λex = 310 nm) for 1, 334 nm (λex = 300 nm) for 2, 379 nm (λex = 352 nm)
for 3, 381 nm (λex = 320 nm) for 5, 343 nm (λex = 305 nm) for 6. Compared to the
pꢀBrPhH3IDC ligand, compounds 1 to 3, 5 and 6 all indicate weak luminescence, which is
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attributed to the π*
→
n transition.24 Since Ca(II), Sr(II), Zn(II) and Cd(II) ions are difficult to
oxidize or to reduce due to their features of electronic configurations, the emission bands of
the related complexes are neither metalꢀtoꢀligand charge transfer (MLCT) nor ligandꢀtoꢀmetal
charge transfer (LMCT) in nature. The emission band of 2 shows relatively stronger
luminescence than other four compounds. It is possible that various factors devoted to this
phenomenon, for instance, the π
→π transition or their coordination to the metal ions resulting
in a decrease in the nonradiative decay of intraligand excited states. Unfortunately, the
polymer 4 shows very weak emissions, it is visible that Co2+ shows fluorescence quenching
for the pꢀBrPhH3IDC ligand.
Figure 8. The solidꢀstate photoluminescent spectra of polymers 1-6 at room temperature.
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CONCLUSIONS
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In summary, we have successfully synthesized and characterized a series of metalꢀorganic
architectures by using pꢀBrPhH3IDC as bridging ligand under hydro(solvo)thermal conditions.
Their molecular structures have been characterized by singleꢀcrystal Xꢀray diffraction,
elemental analyses, thermal analyses, and IR spectra. It was found that the structures of the
polymer 1ꢀ6 are ranging from 1D to 3D frameworks. The strong coordination ability and
various coordination modes of the newly designed imidazole dicarboxylate ligand,
pꢀBrPhH3IDC can be confirmed from both theoretical and experimental aspects. That is to say,
the imidazole dicarboxylate compound bearing pꢀbromidephenyl group at the 2ꢀposition still
shows interesting coordination features. Our study shows that it is an effective way to modify
organic ligands to get different structural complexes. In addition, the thermal investigation of
the complexes demonstrates that they have different thermal behaviors. Obviously, to obtain
more useful information about the coordination ability of the pꢀBrPhH3IDC ligand, and to
prepare more related MOFs with intriguing structures, we need to do more work.
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ASSOCIATED CONTENT
Supporting Information
Crystallographic data in CIF and pdf formats. This material is available free of charge via
the Internet at http://pubs.acs.org/.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: gangli@zzu.edu.cn.
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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We gratefully acknowledge the financial support by the National Natural Science
Foundation of China (21071127, 20501017, and J0830412), and Program for New Century
Excellent Talents in University (NCETꢀ10ꢀ0139) and the Natural Science Foundation of
Henan Education Department (2009A150028 and 2011A150029).
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REFERENCES
(1) (a) Leininger, S.; Olenyuk, B.; Stang, P. J. Chem. Rev. 2000, 100, 853ꢀ908. (b) Moulton, B.;
Zaworotko, M. J. Chem. Rev. 2001, 101, 1629ꢀ1658. (c) Janiak, C. Dalton Trans. 2003, 2781ꢀ2804. (d)
Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004, 43, 2334ꢀ2375. (e) Steel, P. J. Acc.
Chem. Res. 2005, 38, 243ꢀ250. (f) Cheng, J. K.; Chen, Y. B.; Wu, L.; Zhang, J.; Wen, Y. H.; Li, Z. J.;
Yao, Y. G. Inorg. Chem. 2005, 44, 3386ꢀ3388. (g) Maes, M.; Alaerts, L.; Vermoortele, F.; Ameloot,
R.; Couck, S.; Finsy, V.; Denayer, J. F. M. J. Am. Chem. Soc. 2010, 132, 2284ꢀ2292. (i) Sculley, J.;
Yuan, D.; Zhou, H.ꢀC. Energy Environ. Sci. 2011, 4, 2721ꢀ2735. (j) Lu, Z.Z.; Zhang, R.; Li, Y.Z.; Guo,
Z.J.; Zheng, H.ꢀG. J. Am. Chem. Soc. 2011, 133, 4172ꢀ4174. (k) Zhong, D. C.; Deng, J. H.; Luo, X. Z.;
Liu, H. J.; Zhong, J. L.; Wang, K. J.; Lu,T. B. Cryst. Growth Des. 2012, 12, 1992ꢀ1998. (l) Zhou, X.P.;
Li, M.; Liu, J.; Li, D. J. Am. Chem. Soc. 2012, 134, 67ꢀ70.
(2) (a) Bradshaw, D.; Prior, T. J.; Cussen, E. J.; Claridge, J. B.; Rosseinsky, M. J. J. Am. Chem. Soc. 2004,
126, 6106ꢀ6114. (b) Li, J.ꢀR.; Kuppler, R. J.; Zhou, H.ꢀC. Chem. Soc. Rev. 2009, 38, 1477ꢀ1504. (c)
Perman, J. A.; Zaworotko, M. J. Chem. Soc. Rev. 2009, 38, 1400ꢀ1417. (d) Furukawa, H.; Ko, N.;
Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A. O.; Snurr, R. Q.; O ’Keeffe, M.; Kim, J.; Yaghi, O. M.
Science 2010, 329, 424ꢀ428. (e) Pachfule, P.; Das, R.; Poddar, P.; Banerjee, R. Inorg. Chem. 2011, 50,
3855ꢀ3865. (f) Sharma, M. K.; Senkovska, I.; Kaskel, S.; Bharadwaj, P. K. Inorg. Chem. 2011, 50,
539ꢀ544. (g) He, Y.; Zhang, Z.; Xiang, S.; Wu, H.; Fronczek, F. R.; Zhou, W.; Krishna, R.; O’Keeffe,
M.; Chen, B. Chem. A. Eur. J. 2012, 18, 1901ꢀ1904. (h) Sumida, K.; Rogow, D. L.; Mason, J. A.;
McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T.ꢀH.; Long, J. R. Chem. Rev. 2012, 122, 724ꢀ781.
(3) (a) Zheng, S.ꢀL.; Zhang, J.ꢀP.; Wong, W.ꢀT.; Chen, X.ꢀM. J. Am. Chem. Soc. 2003, 125, 6882ꢀ6883. (b)
Coronado, E.; Day, P. Chem. Rev. 2004, 104, 5419ꢀ5448. (c) Radislar A.; Mirsky, V. M. Chem. Rev.
2008, 108, 770ꢀ813. (d) Du, Y.; Chen, C.G.; Wang, E. Anal. Chem. 2010, 82, 1556ꢀ1563. (e) Radislav
23
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Page 24 of 30
1
2
3
4
5
6
A.; Potyrailo; Surman, C.; Nagraj, N.; Burns, A. Chem. Rev. 2011, 111, 7315ꢀ7354. (f) Zhang, J.Z. J.
Phys. Chem. Lett. 2012, 3, 1806ꢀ1807.
7
8
9
(4) (a) Zhao, J.A.; Mi, L.W.; Hu, J.Y.; Hou, H.W.; Fan, Y. T. J. Am. Chem. Soc. 2008, 130, 15222ꢀ15223.
(b) Prasad, T. K.; Hong, D. H.; Suh, M. P. Chem. Eur. J. 2010, 16, 14043ꢀ14050. (c) Aijaz, A.; Lama,
P.; Bharadwaj, P. K. Inorg. Chem. 2010, 49, 5883ꢀ5889. (d) Zhang, Z.ꢀJ.; Shi, W.; Niu, Z.; Li, H.ꢀH.;
Zhao, B.; Cheng, P.; Liao, D.Z.; Yan, S.P. Chem. Commun. 2011, 47, 6425ꢀ6427. (e) Yao, Q.; Sun, J.;
Li, K.; Su, J.; Peskov, M. V.; Zou, X. Dalton Trans. 2012, 41, 3953ꢀ3955.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(5) (a) Hollingsworth, R.I. J. Am. Chem. Soc. 2004, 126, 5927ꢀ5928. (b) Wang, C.D.; Wang, W. M. J.
Chem. Edu. 2011, 88, 299–300. (c) Jamróz, M. H.; Rode, J. E.; Lipiński, P. F. J.; Dobrowolski, J. C. J.
Chem. Inf. Model. 2012, 52, 1462–1479. (d) Elgavi, H.; Krekeler, C.; Berger, R.; Avnir, D. J. Phys.
Chem. C 2012, 116, 330–335.
(6) (a) Wernsdorfer, W.; AliagaꢀAlcalde, N.; Hendrickson, D. N.; Christou, G. Nature. 2002, 416,
406ꢀ409. (b) Wang, X.Y.; Wang, Z.M.; Gao, S. Chem. Commun. 2008, 281ꢀ294. (c) Zeng, Y. F.; Hu,
X.; Liu, F. C.; Bu, X. H. Chem. Soc. Rev. 2009, 38, 469ꢀ480. (d) Wu, D.; Guo, D.; Song, Y.; Huang,
W.; Chunying, D.; Meng, Q.; Sato, O. Inorg. Chem. 2009, 48, 854ꢀ860. (e) Bhargavi, G.;
Rajasekharan, M. V.; Costes, J.; Tuchagues, J. Polyhedron 2009, 28, 1253ꢀ1260.
(7) (a) Seo, J. S.; Whang, D.; Lee, H.; Jun, S. I.; Oh, J.; Jeon, Y. J.; Kim, K. Nature 2000, 404, 982ꢀ986.
(b) Horike, S.; Dinca ̆, M.; Tamaki, K.; Long, J. R. J. Am. Chem. Soc. 2008, 130, 5854ꢀ5855. (c) Lee,
J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Chem. Soc. Rev. 2009, 38,
1450ꢀ1459. (e) Zou, R.ꢀQ.; Sakurai, H.; Han, S.; Zhong, R.ꢀQ.; Xu, Q. J. Am. Chem. Soc. 2007, 129,
8402ꢀ8403. (f) Das, R. K.; Aijaz, A.; Sharma, M. K.; Lama, P.; Bharadwaj, P. K. Chem. Eur. J. 2012,
18, 6866ꢀ6872.
(8) (a) Zou, R.ꢀQ.; Zhong, R.ꢀQ.; Du, M.; Pandey, D. S.; Xu, Q. Cryst. Growth Des. 2008, 8, 452ꢀ459. (b)
Swavey, S.; Swavey, R. Coord. Chem. Rev. 2009, 253, 2627ꢀ2638. (c) Du, M.; Jiang, X. J.; Zhao, X. J.
Inorg. Chem. 2007, 46, 3984ꢀ3995. (d) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T.
Chem. Soc. Rev. 2009, 38, 1330ꢀ1352. (e) Plessis, M. D.; Barbour, L. J. Dalton Trans. 2012, 41,
3895ꢀ3898. (f) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Chem. Rev. 2012, 112, 1126ꢀ1162. (g) Sun, X.L.;
Wang, Z.J.; Zang, S.Q.; Du, C.X. Cryst. Growth Des. 2012, 10, 1021ꢀ1024.
(9) (a) Batten, S. R. CrystEngComm 2001, DOI:10.1039/b010108g. (b) Carlucci, L.; Ciani, G.; Proserpio,
D. M. Coord. Chem. Rev. 2003, 246, 247ꢀ289. (c) Ke, X.ꢀJ.; Li, D.ꢀS.; Miao, D. Inorg. Chem.
24
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Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Commun. 2011, 14, 788ꢀ803. (d) Tanaka, K.; Oda, S.; Shiro, M. Chem. Commun. 2008, 820ꢀ822. (e)
Yin, P. X.; Li, Z. J.; Zhang, J.; Zhang, L.; Lin, Q. P.; Qin, Y. Y.; Yao, Y. G. CrystEngComm 2009, 11,
2734ꢀ2738. (f) Xie, Z.; Ma, L.; Dekra fft, K. E.; Jin, A.; Lin, W. J. Am. Chem. Soc. 2010, 132,
922ꢀ923. (g) Zheng, B.; Bai, J.; Duan, J.; Wojtas, L.; Zaworotko, M. J. J. Am. Chem. Soc. 2011, 133,
748ꢀ745. (h) Yang, J. X.; Zhang, X.; Cheng, J. K.; Zhang, J.; Yao, Y. G.Cryst. Growth Des. 2012, 12,
333ꢀ345.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(10) (a) Pan, L.; Sander, M. B.; Huang, X.; Li, J.; Smith, M.; Bittner, E.; Bockrath, B.; Johnson, J. K. J. Am.
Chem. Soc. 2004, 126, 1308ꢀ1309. (b) Papaefstathiou, G. S.; Georgiev, I. G.; Friščić, T.; MacGillvray,
L. R. Chem. Commun. 2005, 3974ꢀ3976. (c) Xiang, S.; Wu, X.; Zhang, J.; Fu, R.; Hu, S.; Zhang, X. J.
Am.Chem. Soc. 2005, 127, 16352ꢀ16353. (d) Tan, H. Q.; Li, Y. G.; Zhang, Z. M.; Qin, C.; Wang, X.
L.; Wang, E. B.; Su, Z. M. J. Am. Chem. Soc. 2007, 129, 10066ꢀ10067. (d) Pang, H. J.; Peng, J.;
Zhang, C. J.; Li, Y. G.; Zhang, P. P.; Ma, H. Y.; Su, Z. M. Chem. Commun. 2010, 46, 5097ꢀ5099. (e)
Niu, J. Y.; Chen., G.; Zhao, J. W.; Ma, P. T.; Li, S. Z.; Wang, J. P.; Li, M. X.; Bai, Y.; Ji, B. S. Chem.
Eur. J. 2010, 16, 7082ꢀ7086. (f) Liu, H. Y.; Wu, H; Yang., J; Liu, Y. Y.; Ma, J. F.; Liu, H. Y. Cryst.
Growth Des. 2011, 11, 1786ꢀ1797.
(11) (a) Wang, Y. T.; Fan, H. H.; Wang, H. Z.; Chen, X. M. Inorg. Chem. 2005, 44, 4148ꢀ4150. (b)
Carballoa, R.; Coveloa, B.; Lópeza, E. M. V.; Martíneza, E. G.; Castiñeirasb, A.; Niclósc, J. Z. Anorg.
Allg. Chem. 2005, 631, 785ꢀ792. (c) Reger, D. L.; Watson, R. P.; Smith, M. D. Inorg. Chem. 2006, 45,
10077ꢀ10087. (d) Luo, F.; Che, Y. X. ; Zheng, J. M. Cryst. Growth Des. 2009, 9, 1066ꢀ1071.
(12) (a) Shin, D. M.; Lee, I. S.; Cho, D.; Chung, Y. K. Inorg. Chem. 2003, 42, 7722ꢀ7724. (b) Lee, I. S.;
MokShin, D.; Chung, Y. K. Chem. Eur. J. 2004, 10, 3158ꢀ3865. (c) Lu, X. Q.; Jiang, J. J.; Chen, C. L.;
Kang, B. S.; Su, C. Y. Inorg. Chem. 2005, 44, 4515ꢀ4521. (d) Wu, S. T.; Long, L. S.; Huang, R. B.;
Zheng, L. S. Cryst. Growth Des. 2007, 7, 1746ꢀ1752. (e) Sarma, R.; Kalita, D.; Baruah, J. B. Dalton
Trans. 2009, 7428ꢀ7436. (f) Wang, Z. W.; Ji, C. C.; Li, J.; Guo, Z. J.; Li, Y. Z.; Zheng, H. G. Cryst.
Growth Des. 2009, 9, 475ꢀ482. (g) Kanoo, P.; Gurunatha, K. L.; Maji, T. K. Cryst. Growth Des. 2009,
9, 4147ꢀ4156.
(13) (a) Wang, Y.ꢀL.; Yuan, D.ꢀQ.; Bi, W.ꢀH.; Li, X.; Li, X.ꢀJ.; Li, F.; Cao, R. Cryst. Growth Des. 2005, 5,
1849ꢀ1855. (b) Lu, W.ꢀG.; Su, C.ꢀY.; Lu, T.ꢀB.; Jiang, L.; Chen, J.ꢀM. J. Am. Chem. Soc. 2006, 128,
34ꢀ35. (c) Gu, Z.ꢀG.; Cai, Y.ꢀP.; Fang, H.ꢀC.; Zhou, Z.ꢀY.; Thallapally, P. K.; Tian, J.; Liu, J.; Exarhos,
G. J. Chem. Commun. 2010, 46, 5373ꢀ5375. (d) Gu, Z.ꢀG.; Fang, H.ꢀC.; Yin, P.ꢀY.; Tong, L.; Yin, Y.;
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5
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7
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9
Hu, S.ꢀJ.; Li, W.ꢀS.; Cai, Y.ꢀP. Cryst. Growth Des. 2011, 11, 2220ꢀ2227. (e) Feng, X.; Zhao, J. S.; Liu,
B.; Wang, L. Y.; Ng, S.; Zhang, G.; Wang, J. G.; Shi, X. G.; Liu, Y. Y. Cryst. Growth Des. 2010, 10,
1399ꢀ1408. (f) Zheng, S. R.; Cai, S. L.; Fan, J.; Xiao, T. T.; Zhang, W. G. Inorg. Chem. Commun.
2011, 14, 1097ꢀ1101. (g) Dang, F. F.; Wang, X. W.; Han, G. P. Yao, Y. H. Monatsh. Chem. 2009, 140,
615ꢀ617.
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17
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60
(14) (a) Deng, J. H.; Zhong, D. C.; Luo, X. Z.; Liu, H. J.; Lu, T. B. Cryst. Growth Des. 2012, 12,
4861ꢀ4869. (b) Zhang, X. F.; Deng, Z.P.; Huo, L. H.; Feng, Q. M.; Gao, S. Eur. J. Inorg. Chem. 2012,
33, 5506ꢀ5514. (c) Zhao, X.; Ye, X. P.; Chang, M.; Chen, C. J.; Gao, J. Y.; Yue, S. T.; Cai, Y. P. Inorg.
Chem. Commun. 2012,25,96 ꢀ102. (d) Aaramulu, K.; Reddy, S. K.; Hazra, A.; Balasubramanian, S.;
Maji, T. K. Inorg. Chem. 2012, 51, 7103ꢀ7111. (e) Gu, Z. G.; Li, G. Z.; Yin, P. Y.; Chen, Y. N.; Peng,
H. M.; Wang, M. F.; Cheng, F.; Gu, F. L.; Li, W. S.; Cai, Y. P. Inorg. Chem. Commun. 2011, 14,
1479ꢀ1484. (f) Yuan, G.; Shao, K. Z.; Du, D. Y.; Wang, X. L.; Su, Z. M.; Ma, J. F. CrystEngComm
2012, 14, 1865ꢀ1873. (g) Das, S.; Saha, D.; Ardanya, S.; Baitalik, S. Dalton Trans. 2012, 41,
12296ꢀ12310.
(15) (a) Wang, W.ꢀY.; Niu, X.ꢀL.; Gao, Y.ꢀC.; Zhu, Y.ꢀY.; Li, G.; Lu, H.ꢀJ.; Tang, M.ꢀS. Cryst. Growth
Des. 2010, 10, 4050ꢀ4059. (b) Wang, W.ꢀY.; Yang, Z.ꢀL.; Wang, C.ꢀJ.; Lu, H.ꢀJ.; Zang, S.ꢀQ.; Li, G.
CrystEngComm 2011, 13, 4895ꢀ4902. (c) Zhu, Y.; Wang, W. ꢀY.; Guo, M. ꢀW.; Li, G.; Lu, H. ꢀJ.
Inorg. Chem. Commun. 2011, 14, 1432ꢀ1435. (d) Zhang, F.ꢀW.; Li, Z.ꢀF.; Ge, T.ꢀZ.; Yao, H.ꢀC.; Li,
G.; Lu, H.ꢀJ.; Zhu, Y.ꢀY. Inorg. Chem. 2010, 49, 3776ꢀ3788. (e) Li, Z. F.; Luo, X. B.; Gao, Y. C.; Lu,
H. J.; Li, G. Inorg. Chim. Acta 2012, 384, 352ꢀ356. (f) Wang, C. J.; Wang, T.; Zhang, W.; Lu, H. J.;
Li, G. Cryst. Growth Des. 2012, 12, 1091ꢀ1094. (g) Cao, X. J.; Zhang, J.; Wang, C. J.; Zhu, Y. Y.; Li,
G. CrystEngComm 2012, 1–12. (h) Guo, M. W.; Chen, N.; Yue, Z. F.; Zhang, Y.; Li, G.
CrystEngComm 2012, 14, 4955ꢀ4958. (i) Cao, X. J.; Zhang, J.; Wang, C. J.; Zhu, Y. Y.; Li, G.
CrystEngComm 2012, 14, 4357ꢀ4368. (j) Cao, X. J.; Liu, Y.; Wang, L. Y.; Li, G. Inorg. Chim. Acta
2012, 392, 16ꢀ24. (k) Zhang, Y.; Luo, X. B.; Yang, Z. L.; Li, G. CrystEngComm 2012, 14, 7382ꢀ7397.
(16) Lebedev, A. V.; Lebedeva, A. B.; Sheludyakov, V. D.; Kovaleva, E.A.;Ustinova,O. L.; Shatunov, V. V.
Russ. J. Gen. Chem. 2007, 77, 949ꢀ953.
(17)Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.;
Montgomery, J. A.; Vreven, T. J.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.;
Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada,
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1
2
3
4
5
6
7
8
9
M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.;
Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.;
Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.;
Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A.
D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Clifford, A. G.; Baboul, S.; Cioslowski, J.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.;
AlꢀLaham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen,
W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. GAUSSIAN 03, Revision C. 02, Gaussian, Inc.
Wallingford, CT, 2004 (SN: Pople, PC21390756Wꢀ4203N).
10
11
12
13
14
15
16
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18
19
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21
22
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45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(18) (a) Sheldrick, G. M. SHELXꢁ97, Program for the Solution and Refinement of Crystal Structures,
University of Göttingen, Germany, 1997. (b) Sheldrick, G. M. Acta Crystallogr. Sect. A: Found.
Crystallogr. 2008, A64, 112−122.
(19) (a) Volkringer, C. Loiseau, T. Cryst. Growth Des. 2008, 8 ,685–689. (b) Pachfule, P.; Das, R.; Poddar,
P.; Banerjee, R. Cryst. Growth Des. 2011, 11, 1215–1222. (c) Srinivasu, K.; Ghosh, S.K. J. Phys.
Chem. C. 2011, 115, 16984–16991. (d) Plonka, A. M.; Banerjee, D.; Banerjee, J. B. Cryst. Growth
Des. 2012, 12, 2460ꢀ2467. (e) Vakiti, R. K.; Garabato, B. D.; Schieber, N. P.; Cao, Y.; Maddox, J. B.;
Pan, W. P.; Yan, B. B. Cryst. Growth Des. 2012, 12, 3937–3943. (f) Zhang, X.; Huang, Y. Y.; Zhang,
M. J.; Zhang, J.; Yao, Y. G. Cryst. Growth Des. 2012, 12, 3231ꢀ3238. (g) Schoenecker, P. M.; Carson,
C. G.; Jasuja, H.; Walton, K. S. Ind. Eng. Chem. Res. 2012, 5, 6513–6519. (h) Gu, Z. G.; Liu, Y. T.;
Hong, X. J.; Li, W. S.; Hu, S. J.; Cai, Y. P. Cryst. Growth Des. 2012, 12, 2178ꢀ2186.
(20) Addison, A. A. W.; Rao, T. N.; Reedjik, J.; Verschoor, G. C. J. J. Chem. Soc., Dalton Trans. 1984,
1349ꢀ1356.
(21) (a) Wang, Y.ꢀL.; Yuan, D.ꢀQ.; Bi, W.ꢀH.; Li, X.; Li, X.ꢀJ.; Li, F.; Cao, R. Cryst. Growth Des. 2005, 5,
1849ꢀ1855. (b) Wen, L.ꢀL.; Wang, D.ꢀE.; Chen, Y.ꢀJ.; Meng, X.ꢀG.; Li, D.ꢀF.; Lan, S.ꢀM. J. Coord.
Chem. 2009, 62, 789ꢀ796. (c) Li, C.ꢀJ.; Hu, S.; Li, W.; Lam, C.ꢀK.; Zheng, Y.ꢀZ.; Tong, M.ꢀL. Eur. J.
Inorg. Chem. 2006, 1931ꢀ1935. (d) Xie, L.ꢀX.; Hou, X.ꢀW.; Fan, Y.ꢀT.; Hou, H.ꢀW. Cryst. Growth Des.
2012, 12, 1282ꢀ1291.
(22) (a) Wang, S.; Zhang, L. R.; Li, G. H.; Huo Q. S. and Liu, Y. L. CrystEngComm 2008, 10, 1662ꢀ1666.
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Page 28 of 30
1
2
3
4
(b) Fang, R.ꢀQ.; Zhang, X.ꢀM. Inorg. Chem. 2006, 45, 4801ꢀ2810.
5
6
7
8
(23) (a) Wu, Y. P.; Li, D. S.; Fu, F.; Dong, W. W.; Zhao, J.; Zou, K.; Wang, Y. Y. Cryst. Growth Des. 2011,
11, 3850–3857. (b) Jia, W. W.; Luo, J. H.; Zhu, M. L. Cryst. Growth Des. 2011, 11, 2386–2397. (c)
Zhang, M. D.; Di, C. M.; Qin, L.; Qin, X. Q.; Li, Y. Z.; Guo, Z. J. Zheng, H. G. Cryst. Growth Des.
2012, 12, 3957−3963.
9
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25
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54
55
56
57
58
59
60
(24) (a) Chen, Z. L.; Jiang, C. F.; Yan, W. H.; Liang, F. P.; Batten, S. R. Inorg. Chem., 2009, 48, 4674–4684.
(b) Mu, Y. J.; Fu, J. H.; Song, Y. J.; Li, Z.; Hou, H. W.; Fan, Y. T. Cryst. Growth Des. 2011, 11,
2183–2193. (c) Ma, L. F.; Han, M. L.; Qin, J. H.; Wang, L. Y.; Du, M. Inorg. Chem., 2012, 51,
9431–9442. (d) Qin, L.; Hu, J.S.; Li, Y.Z.; Zheng, H.G. Cryst. Growth Des. 2012, 12, 403–413.
(25) (a) Pan, L.; Frydel, T.; Sander, M.B.; Huang, X.; Li, J. Inorg. Chem. 2001, 40, 1271ꢀ1283. (b) Ghosh,
A.; Rao, K. P.; Sanguramath, R. A.; Rao, C. N. R. J. Mol. Struct. 2009, 927, 37ꢀ42.
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Table 1. Crystal data and structure refinement information for compounds 1-6
1
2
3
4
5
6
Formula
C11H9BrN2O6Ca
385.19
C11H7BrN2O5Sr
414.72
C11H7BrN2O5Zn
392.46
C22H16BrN4O10Co
715.14
C22H13Br2N4O9Cd1.5 C32H26Br2N6O12Cd2
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
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30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
Fw
805.78
1071.13
Crystal system
Crystal size/mm
Monoclinic
0.20 × 0.18 × 0.14
Monoclinic
0.22 × 0.20 × 0.20
P21/c
Orthorhombic
0.20 × 0.18 × 0.08
Monoclinic
0.35 × 0.22 × 0.20
Triclinic
0.17 × 0.16 × 0.13
Tetragonal
0.20 × 0.20 × 0.20
I41/a
Space group
a / Å
P21/c
Ama/2
12.8977(7)
8.1974(3)
11.2059(4)
90
P21/c
Pī
15.4496(9)
6.9102(4)
12.9227(7)
90
14.8833(17)
6.6486(8)
12.8054(15)
90
9.8824(15)
13.760(2)
9.9776
90
8.7083(7)
10.1660(7)
14.8129(11)
74.9950(10)
89.9150(10)
72.9700(10)
1207.18(16)
2.217
21.9976(6)
21.9976(6)
16.5598(9)
90
b / Å
c / Å
α
β
γ
/ °
/ °
/°
102.908(6)
90
103.0520(10)
90
90
113.223(2)
90
90
90
90
V / Å3
Dc / Mg mꢀ3
1344.77(13)
1.903
1234.4(3)
2.232
1184.77(9)
2.195
1246.9(3)
1.905
8013.2(5)
1.759
Z
4
4
4
2
2
8
/ mmꢀ1
3.467
7.626
5.467
3.958
4.706
3.119
ꢀ
Reflns collected/unique
5628 / 2755
R(int) = 0.0426
2755/4/221
9948/ 2526
R(int) = 0.0457
2526 / 0 / 209
1587 / 893
R(int) = 0.0247
893/2/102
8238 / 3083
R(int) = 0.0258
3083 / 0 / 210
9935/ 4685
R(int) = 0.0183
4685 / 0 / 351
20976/ 3739
R(int) = 0.0672
3739 / 0 / 234
Data/restraints/parameters
R
Rw
0.0622
0.1008
1.025
0.0454
0.0873
0.876
0.0329
0.0734
1.087
0.0340
0.0759
1.102
0.0343
0.0747
1.044
0.0470
0.0940
1.034
GOF on F2
ꢁρmin and ꢁρ
max, e Åꢀ3
ꢀ0.69 and 0.69
ꢀ0.538 and 0.543
ꢀ0.51 and 0.51
ꢀ0.699 and 0.444
ꢀ1.430 and 1.172
ꢀ0.999 and 1.108
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