Construction and Properties of Six MetalâOrganic Frameworks

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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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Crystal Growth & Design

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, Gang Li*

College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, Henan, P. R. China

ABSTRACT: The newly designed organic ligand, 2-(p-bromophenyl)-1H-imidazole-4,5-dicarboxylic acid (p-BrPhH3IDC) has been successfully prepared and explored its coordination features. By the reactions of p-BrPhH3IDC with main group or transition metals, six metal-organic frameworks, namely, [Ca(p-BrPhHIDC)(H2O)2]n

(1),

{[Co(p-BrPhH2IDC)2]·2H2O}n

[Sr(p-BrPhHIDC)(H2O)]n (4),

(2),

[Zn(p-BrPhHIDC)(H2O)]n

[Cd1.5(p-BrPhHIDC)(p-BrPhH2IDC)(H2O)]n

(5)

(3), and

{[Cd2(p-BrPhHIDC)2(4,4′-bipy)]⋅4H2O}n (4,4′-bipy = 4,4′-bipyridine) (6) have been synthesized under hydro(solvo)thermal conditions. X-ray single-crystal analyses reveal that they have rich structural chemistry ranging from one-dimensional (1D) (3), two-dimensional (2D) (1, 2, 4 and 5) to three-dimensional (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 solid-state supramolecular structures of polymers 3, 4 and 5. The solid-state photoluminescence properties of the polymers 1-6 have been investigated as well.

INTRODUCTION In the last two decades, more and more researchers pay attention to the construction of various metal-organic 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. E-mail: [email protected]. Fax: +86-371-67781764. 1

ACS Paragon Plus Environment


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architectures and fascinating topologies.9 Among them, zero-dimensional (0D) multinuclear complexes, one-dimensional (1D) helical and zigzag chains, two-dimensional (2D) grids, three-dimensional (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 metal-to-ligand 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, imidazole-4,5-dicarboxylic acid (H3IDC) and its 2-position 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 Recently, our group is interested in designing and preparing the H3IDC derivatives bearing aromatic groups at the 2-position 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,

2-phenyl-1H-imidazole-4,5-dicarboxylic

acid

(PhH3IDC),

2-(2-naphthyl)-1H-imidazole-4,5-dicarboxylic

acid

(NH3IDC),

2-(p-methylphenyl)-1H-imidazole-4,5-dicarboxylic

acid

(p-MePhH3IDC),

2-(p-hydroxylphenyl)-1H-imidazole-4,5-dicarboxylic

acid

2-(3,4-dimethylphenyl)-1H-imidazole-4,5-dicarboxylic 2-p-methoxyphenyl-1H-imidazole-4,5-dicarboxylic

acid

acid

(p-OHPhH3IDC), (DMPhH3IDC)

(MOPhH3IDC)

have

and 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 electron-withdrawing group, bromine to phenyl unit and obtain a new organic ligand 2-(p-bromophenyl)-1H-imidazole-4,5-dicarboxylic acid (p-BrPhH3IDC), 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(p-BrPhHIDC)(H2O)2]n (1), [Sr(p-BrPhHIDC)(H2O)]n (2), [Zn(p-BrPhHIDC)(H2O)]n

(3),

{[Co(p-BrPhH2IDC)2]·2H2O}n

(4), 2


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(5)

and

{[Cd2(p-BrPhHIDC)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 two-dimensional (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 p-BrPhH3IDC ligand exhibits abundant coordination modes (Scheme 2), which confirms the theoretical prediction. Finally, the solid-state photoluminescence properties of polymers 1-6 have been investigated at room temperature as well. Scheme 1.

Syntheses of Complexes 1-6 Ca(NO3)2.4H2O H2O NaOH 150 C 96 h

[Ca(p-BrPhHIDC)(H2O)2]n

1 2D

Sr (NO3)2 CH3CN/H2O Et3N 150 C 96 h

[Sr(p-BrPhHIDC)(H2O)]n

2 2D

Zn(NO3)2 . 6H2O CH3OH/H2O Et3N 160 C 72 h

[Zn(p-BrPhHIDC)(H2O)]n

3 1D

O

HOOC

COOH

O

N

NH

O

+

Co (NO3)2. 6H2O {[Co(p-BrPhH2IDC)2] . 2H2O}n CH3OH/H2O Et3N 160 C 72 h

4 2D

O

Cd(NO3)2.4H2O Br

O

CH3CN/H2O Et3N 160 C 72 h

p-BrPhH3IDC

Cd(NO3)2 .4H2O + 4,4 '-bipy CH3CN/H2O Et3N 160 C 72 h O


5 2D

{[Cd2(p-BrPhHIDC)2(4,4' -bipy)] ¡¤4H2O}n

6

3D

Scheme 2. Coordination Modes of the p-BrPhH3IDC ligand M

M M

O

O

HN

M

N

O

O

M

M

O

O

O

O

O M

M

HN

M

N

O O

O N

M

N

Br

Br

Br

a

b

c

M

M O

OH

O

O M

HN

N

Br

d

M

O

O

HN

N

O

HO

Br

e

M

OH

O

N

N

O

O M

M

M

OH

O

N

N

O

O M

Br

Br

f

g

M

3



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EXPERIMENTAL SECTION Materials. All chemicals are of reagent grade quality obtained from commercial sources and used without further purification. The organic ligand p-BrPhH3IDC was prepared according to literature procedure.16 The C, H and N microanalyses were carried out on a FLASH EA 1112 analyzer. IR spectra were recorded on a Nicolet NEXUS 470-FTIR spectrophotometer as KBr pellets in the 400-4000 cm-1 region. Fluorescence spectra were characterized at room temperature by an F-4500 fluorescence spectrophotometer. The optimized geometry and natural bond orbital (NBO) charge distribution of the free ligand p-BrPhH3IDC were given by the GAUSSIAN 03 suite of programs. And all calculations were carried out at the B3LYP/6-311++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), p-BrPhH3IDC (15.6 mg, 0.05 mmol), and H2O (7 mL), NaOH (40 mg, 0.5 mmol) were sealed in 25 mL Teflon-lined 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 flake-shaped 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 (cm-1, 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), p-BrPhH3IDC (15.6 mg, 0.05 mmol), and CH3CN/H2O (3/4, 7 mL), Et3N (0.056 mL, 0.4 mmol) were sealed in 25 mL Teflon-lined 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 (cm-1, 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), 4


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669 (w), 518 (m), 435 (w). Preparation of [Zn(p-BrPhHIDC)(H2O)]n (3). A mixture of Zn(NO3)2⋅4H2O (14.9 mg, 0.05 mmol), p-BrPhH3IDC (15.6 mg, 0.05 mmol), Et3N (0.056 mL, 0.4 mmol) and CH3OH/H2O (3/4, 7 mL) were sealed in 25 mL Teflon-lined 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 block-shaped 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 (cm-1, 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). Preparation of {[Co(p-BrPhH2IDC)2]·2H2O}n (4). A mixture of p-BrPhH3IDC (15.6 mg, 0.05 mmol), Co(NO3)2·6H2O (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 Teflon-lined 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 cubic-shape 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 (cm-1, 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 Teflon-lined 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 club-shaped 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 (cm-1, 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, 5



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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 Teflon-lined 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 (cm-1, 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). Crystal Structure Determinations. Crystal data and experimental details for the compounds 1-6 are contained in Table 1. Measurements of 1-6 were made on a Bruker smart APEXII CCD diffractometer with a graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å). Single crystals of 1-6 were selected and mounted on a glass fiber. All data were collected at room temperature using the ω-2θ scan technique and corrected for Lorenz-polarization effects. A correction for secondary extinction was applied. The six structures were solved by direct methods and expanded using the Fourier technique. The non-hydrogen atoms were refined with anisotropic thermal parameters. Hydrogen atoms were included but not refined. All calculations were performed using the SHELX-97 crystallographic software package.18 Selected bond lengths and angles, and the parameters of hydrogen bonds for 1-6 are listed in Tables S1 and S2, respectively (Supporting Information). CCDC 906073-906078 contain the supplementary crystallographic data for 1-6, 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, p-hydroxylphenyl, 3,4-dimethylphenyl and p-methoxyphenyl in the related imidazole dicarboxylate ligands have been calculated by quantum chemical method, and confirmed by experimental results. The results indicate that as these electron-donor substituted 6


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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 electron-withdrawing groups in the PhH3IDC system, and study their coordination features. Herein, we firstly probe p-bromophenyl substituent effect on the p-BrPhH3IDC ligand by theoretical calculation. The optimized geometry and NBO charge distributions of the free ligand p-BrPhH3IDC have been calculated by the B3LYP/6-311++G(d, p) level.17 The computed results (Scheme 3) display that the free ligand p-BrPhH3IDC has two characteristics: (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 2-p-bromine atom into

p-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 p-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 p-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 imidazole-H and two COO-H units can be deprotonated in the six polymers herein, also leading to the deprotonated p-BrPhH3-nIDCn- (n = 1 or 2) anions. As shown in Scheme 2, the ligand

p-BrPhH3IDC shows various coordination modes. To understand the coordination modes of p-BrPhH3IDC, we have analyzed the the Cambridge Structure Database, and found about more than four hundred complexes bearing H3IDC and its 2-position 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 dicarboxylate-based complexes.15e This suggests that no matter the derivatives of H3IDC contain what kinds of 2-position substituent: electron-withdrawing or electron-donor groups, they all show diversity of 7



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coordination modes. In experimental process, we adopted the ligand p-BrPhH3IDC 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 two-dimensional sheets and the transition-metal polymers 3-6 possess one-dimensional, two-dimensional or three-dimensional structures. 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 1-6. Crystals of 1-6 can be successfully produced in the metal-to-ligand 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 three-dimensional 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 8


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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.

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 p-BrPhH3IDC 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.

Crystal Structures of Crystalline Polymers [Ca(p-BrPhHIDC)(H2O)2]n (1) and [Sr(p-BrPhHIDC)(H2O)]n (2). A pair of polymers 1 and 2 is obtained by the reactions of p-BrPhH3IDC 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 carboxylato-chelating p-BrPhHIDC2- anion, O1 and O2 from one bidentate-chelating carboxylato groups of another p-BrPhHIDC2- anion, and another two monodentate oxygen atoms (O4c and O2b ) from two distinct organic ligands. The Ca-O bonds are in the range of 2.382(2) to 2.714(2) Å (average Ca-O distance being 2.465 Å), which is close to the reported 8-coordinated Ca(II) polymers, [Ca(2,5-PDC)(DMF)]n, [Ca(2,4-PDC)(H2O)]n and [Ca(2,4-PDC)(DMF)]n19d (PDC = Pyridinedicarboxylic acid; average Ca-O distance being 2.46 (±0.08) Å), and also consistent with the related imidazole dicarboxylate 8-coordinated pyridine-dicarboxylic acid {[Ca2(EIDC)2(H2O)2]·H2O}n19h (EH3DIC = 2-ethyl-1H-imidazole-4,5-dicarboxylic acid; average Ca-O 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 9



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In polymer 1, the p-BrPhHIDC2- ligand presents µ4-kO: kO′, O′′: kO′′, O′′′: kO′′′ coordination mode (Scheme 2a). The µ4-p-BrPhHIDC2- ligand bridges neighboring Ca(II) ions to form a 1D chain along the c-direction. The p-BrPhHIDC2- ligands further link the adjacent infinite chains to get a 2D layer (Fig. 1). Furthermore, the layers connected by weak intermolecular π-π 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).

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 p-BrPhHIDC2- 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 p-BrPhHIDC2- anion adopts the same coordination mode,15h µ5-kO: 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 10


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corrugated-shape chains. These adjacent chains are further linked by the O atoms from the carboxyl groups leading to a spectacular 2D grid. 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. By searching the literatures, we found that the Sr(II) polymers bearing the related imidazole dicarboxylate ligands are limited. Only one 3D {[Sr(µ2-PhH2IDC)2(H2O)4]}n13g, three 2D [Sr(EH2IDC)2(H2O)2]n15e, [Sr(PhHIDC)(H2O)]n and [Sr(p-MePhHIDC)(H2O)]n15k 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 X-ray analysis, polymer 3 is an infinite 1D chain. Clearly, each p-BrPhHIDC2- ligand adopts the coordination mode, µ2-kN, O: kN′, O′ (Scheme 2c). The central Zn(II) ion is five-coordinated by two carboxylate oxygen atoms (O1 and O1a), two nitrogen atoms (N1 and N1a) from two individual p-BrPhHIDC2- 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) 11



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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 five-coordinated Zn atom shows that the geometry around the Zn(II) atom is distorted trigonal bipyramidal geometry.20 It is worth noting that the nitrogen atoms from p-BrPhHIDC2- ions link neighboring Zn(II) ions to build up a 1D chain along the c-axis 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 O3-H3⋅⋅⋅Br1a and O3-H3⋅⋅⋅O2b. Obviously, all of the donor oxygen atoms are from the coordinated water molecules, but the acceptor atoms are Br and O from p-BrPhHIDC2- ligands. What’s more, the O3-H3…Br1a bonds increase the stability of the solid-state architecture. Finally, the 3D supramolecular structure is assembled by the weak π-π stacking interactions, the distance between two neighboring phenyl rings and imidazole rings of p-BrPhHIDC2- anion is 8.1974(3) Å (Figure 3b). (a)

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(b)

Figure 3. (a) View of the 1D chain of 3 (H atoms omitted for clarity). (b) Crystal packing diagram of 3 showing the π-π stacking between the adjacent chains (Part of H atoms omitted for clarity).

Crystal Structure of Crystalline Polymer {[Co(p-BrPhH2IDC)2](H2O)2}n (4). The result of single-crystal X-ray diffraction analysis indicates that polymer 4 indicates a 2D framework. As shown in Figure S5, the central Co(II) ion is in a six-coordinated environment, which is completed by four O atoms (O2, O2c, O3a and O3b) and two N atoms (N1 and N1c) from four individual p-BrPhH2IDC- anions. The oxygen atoms (O2, O2c, O3a and O3b) constitute the equatorial plane, with the L-Co-L (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 Co-N bond length is 2.1269(15) Å, which are in the normal values and close to those observed for carboxylate-based cobalt (II) complexes.15f,21 All the p-BrPhH2IDC- ligand in polymer 4 adopt the same coordination mode, µ2-k N, O: k O′ (Scheme 2d), and bridge Co(II) ions to form 1D helical chains: right-handed and left-handed helical chains (Figure 4a). And then the adjacent helical chains are held together by the p-BrPhH2IDC- ligands forming a 2D framework (Figure 4b). Moreover, the four

µ2-BrPhH2IDC- anions join the four Co(II) ions to construct a rhombic grid. Within the grid, 13



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the distance of the Co-Co 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 (N2-H2...O5 2.812 Å, 175° and O-H⋅⋅⋅O (O4-H1⋅⋅⋅O1 2.456 Å, 178°) link these layers to generate an extended 3D supramolecular network (Figure 4c). (a)

(b)

(c)

Figure 4. (a) The 1D right-handed helical and 1D left-handed helical chains. (b) The 2D sheet comprising the infinite helical chains. (c) Crystal packing diagram of 4 showing intermolecular H-bonds and the π-π stacking between the helical chains (Partial H atoms omitted for clarity).

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Crystal

Structures

of

Crystalline


(5)

Polymers and

{[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). As depicted in Figure S6, the crystal unit of 5 contains two crystallographically independent Cd(II) ions, one p-BrPhH2IDC2- anion and two coordinated H2O molecules. Both Cd1 and Cd2 are six-coordinated 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 p-BrPhH2IDC2ligands, another two O6 and O6a atoms from two individual p-BrPhH2IDC2- 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 L-Cd-L 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 p-BrPhH3IDC in polymer 5 can be singly deprotonated or doubly deprotonated forming p-BrPhH3-nIDCn- (n = 1 or 2) anions, which shows two kinds of coordinated modes, namely, µ2- kN, O: kN′, O′ (Scheme 2e) and µ3-KN, O: kN′, O′: kO′′ (Scheme 2f), respectively. The p-BrPhHIDC2- and p-BrPhH2IDC- 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 single-nuclear Cd(II) atoms are staggered linking. Notably, the 2D grid is composed by these chains bridged by

µ3-BrPhHIDC2- 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 solid-state structure (Figure 5c), with the hydrogen bond distances of 2.480(4) 15



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- 2.926(4) Å. X-ray diffraction analysis reveals that complex 6 is a 3D framework. The asymmetric unit of 6 is composed of two Cd(II) ions, two p-BrPhHIDC2- anions, one 4,4′-bipy unit, and four water molecules. As shown in Figure S7, the central Cd(II) ion is located in six-coordinated 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

µ2-p-BrPhHIDC2- 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)–2.456(3) Å and those of Co–N vary from 2.275(3) to 2.333(3) Å. Compared with the polymer 5, the imidazole dicarboxylate ligand in polymer 6 adopts a new coordination mode, µ2-kN, 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 µ2-BrPhHIDC2- 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(p-BrPhHIDC)12(4,4′-bipy)6], the quadrangle are also connected by µ2-p-BrPhHIDC2- ligands. Furthermore, the 1D infinite chains are linked to a 2D grid by nitrogen atoms from bridging imidazole ring (Figure 6b). It is noteworthy that the µ2-4,4′-bipy can pass through the adjacent layers to hold the layers into 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 6-connected nodes which are connected to three µ2-BrPhHIDC and one µ2-4,4′-bipy ligands. Hence, the 3D network of 6 can be described as a 6-connected topology with a point symbol of 3(6).6(6).7(3) 3.3.3.3.3.3.6.6.6.6.6.6. 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 N-donors would enrich the kinds of complexes.23 Also, the N-containing 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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(a)

(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. 17



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(a)

(c)

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(b)

(d)

Figure 6. (a) The infinite chain of 6 built by p-BrPhHIDC2-anions 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 6-connected 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 1-6 show broad absorption bands in the range of 3400–3650 cm-1, which indicates the presence of νN–H and the νO–H stretching frequencies of imidazole rings and coordinated water molecules, respectively. Six complexes exhibit strong characteristic absorptions around the frequency range 1557−1570 cm νas(COO-) and 1450−1485 cm νs(COO-), respectively. The characteristic IR band of the phenyl ring at 840–860 cm-1 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 p-BrPhHIDC2- 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 p-BrPhHIDC2(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 three-stage 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 19



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and two µ-COO- 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 p-BrPhHIDC2- 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 p-BrPhHIDC2- 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%). 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 µ-COO- 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 p-BrPhHIDC2- 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 solid-state photoluminescence properties of complexes 1-6 and the corresponding free p-BrPhH3IDC ligand have been investigated at room temperature (Figure 8). The free p-BrPhH3IDC 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 p-BrPhH3IDC ligand, compounds 1 to 3, 5 and 6 all indicate weak luminescence, which is 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 metal-to-ligand charge transfer (MLCT) nor ligand-to-metal 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 p-BrPhH3IDC ligand.

Figure 8. The solid-state photoluminescent spectra of polymers 1-6 at room temperature.

21



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CONCLUSIONS In summary, we have successfully synthesized and characterized a series of metal-organic architectures by using p-BrPhH3IDC as bridging ligand under hydro(solvo)thermal conditions. Their molecular structures have been characterized by single-crystal X-ray diffraction, elemental analyses, thermal analyses, and IR spectra. It was found that the structures of the polymer 1-6 are ranging from 1D to 3D frameworks. The strong coordination ability and various coordination modes of the newly designed imidazole dicarboxylate ligand, p-BrPhH3IDC can be confirmed from both theoretical and experimental aspects. That is to say, the imidazole dicarboxylate compound bearing p-bromidephenyl group at the 2-position 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 p-BrPhH3IDC ligand, and to prepare more related MOFs with intriguing structures, we need to do more work.

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 *E-mail: [email protected]. Notes The authors declare no competing financial interest.

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ACKNOWLEDGMENTS 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 (NCET-10-0139) and the Natural Science Foundation of Henan Education Department (2009A150028 and 2011A150029).

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Table 1. Crystal data and structure refinement information for compounds 1-6 1

2

3

4

5

6

Formula

C11H9BrN2O6Ca

C11H7BrN2O5Sr

C11H7BrN2O5Zn

C22H16BrN4O10Co

C22H13Br2N4O9Cd1.5

C32H26Br2N6O12Cd2

Fw

385.19

414.72

392.46

715.14

805.78

1071.13

Crystal system Crystal size/mm

Monoclinic 0.20 × 0.18 × 0.14

Orthorhombic 0.20 × 0.18 × 0.08

Monoclinic 0.35 × 0.22 × 0.20

Triclinic 0.17 × 0.16 × 0.13

Space group

P21/c

Monoclinic 0.22 × 0.20 × 0.20 P21/c

Ama/2

P21/c

Pī

Tetragonal 0.20 × 0.20 × 0.20 I41/a

a/Å

15.4496(9)

14.8833(17)

12.8977(7)

9.8824(15)

8.7083(7)

21.9976(6)

b/Å

6.9102(4)

6.6486(8)

8.1974(3)

13.760(2)

10.1660(7)

21.9976(6)

c/Å

12.9227(7)

12.8054(15)

11.2059(4)

9.9776

14.8129(11)

16.5598(9)

α/°

90

90

90

90

74.9950(10)

90

β/°

102.908(6)

103.0520(10)

90

113.223(2)

89.9150(10)

90

90

90

90

90

72.9700(10)

90

1344.77(13)

1234.4(3)

1184.77(9)

1246.9(3)

1207.18(16)

8013.2(5)

Dc / Mg m

1.903

2.232

2.195

1.905

2.217

1.759

Z

4

4

4

2

2

8

µ / mm-1

3.467 5628 / 2755 R(int) = 0.0426 2755/4/221 0.0622 0.1008 1.025 -0.69 and 0.69

7.626 9948/ 2526 R(int) = 0.0457 2526 / 0 / 209 0.0454 0.0873 0.876 -0.538 and 0.543

5.467 1587 / 893 R(int) = 0.0247 893/2/102 0.0329 0.0734 1.087 -0.51 and 0.51

3.958 8238 / 3083 R(int) = 0.0258 3083 / 0 / 210 0.0340 0.0759 1.102 -0.699 and 0.444

4.706 9935/ 4685 R(int) = 0.0183 4685 / 0 / 351 0.0343 0.0747 1.044 -1.430 and 1.172

3.119 20976/ 3739 R(int) = 0.0672 3739 / 0 / 234 0.0470 0.0940 1.034 -0.999 and 1.108

γ /° 3

V/Å

-3

Reflns collected/unique Data/restraints/parameters R Rw GOF on F2 ∆ρmin and ∆ρmax, e Å-3

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Page 30 of 30

Table of Contents Use Only Six Ca(II), Sr(II), Zn(II), Co(II) and Cd(II) imidazole dicarboxylate-based MOFs have been Yu Zhang, Beibei Guo, Li Li, Shaofeng Liu, Gang Li*

hydrothermally prepared and characterized by single-crystal X-ray crystallography. The solid-state photoluminescence properties of the six polymers have been determined as well.

Construction and Properties of Six MOFs Based on the Newly Designed 2-(p-Bromophenyl)-Imidazole Dicarboxylate Ligand

30


Construction and Properties of Six MetalâOrganic Frameworks

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