Two MetalâOrganic Frameworks with Structural Varieties Derived from

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Two Metal-Organic Frameworks with Structural Varieties Derived from CisTrans Isomerism Nodes and Effective Detection of Nitroaromatic Explosives Jiantang Li, Xiaolong Luo, Yue Zhou, Li-Rong Zhang, Qisheng Huo, and Yunling Liu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01726 • Publication Date (Web): 07 Feb 2018 Downloaded from http://pubs.acs.org on February 8, 2018

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Crystal Growth & Design

Two Metal-Organic Frameworks with Structural Varieties Derived from Cis-Trans Isomerism Nodes and Effective Detection of Nitroaromatic Explosives Jiantang Li, Xiaolong Luo, Yue Zhou, Lirong Zhang,* Qisheng Huo and Yunling Liu*

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P. R. China.

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ABSTRACT

Two

novel

(JLU-MOF48,

porous

MOFs,

[Zn5(DpImDC)2(DMF)4(H2O)3]·H2O·DMF H5DpImDC

2-(3,5-dicarboxyphenyl)-1H-imidazole-4,5-dicarboxylic

= acid)

and

[Co5(DpImDC)2(DMF)4(H2O)6]·DMF (JLU-MOF49), have been solvothermally synthesized by using a ligand consists of 4,5-imidazoledicarboxylic acid part and isophthalic acid part. Two compounds have similar structures and connections, but with significant differences in symmetry (monoclinic and orthorhombic) due the cis-trans isomerism in a mononuclear metal node. Moreover, JLU-MOF48 exhibits notable luminescent properties and owns outstanding performance for detecting nitroaromatic explosives, especially for 2,4,6-trinitrophenol (Ksv = 1.0×105 M-1).


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INTRODUCTION

Nowadays, nitroaromatic explosives have become a major threat to social security and the environment, not only for its potential to produce powerful explosive weapons, but also for its great danger to human health. Therefore, rapid detection of nitroaromatic explosives has become an important issue in material chemistry.1-4

Over the years, with the rapid development of porous material chemistry, numerous scientists have devoted themselves to this fascinating field.5 Among this, metal-organic frameworks (MOFs) has become a class of unique materials due to their prominent structural tunability and excellent performance in many fields.6 Countless MOFs have been successfully applied in sensing,7, luminescence,9,

10

magnetism,11,

12

catalysis,13,

14

8

gas adsorption and

separation,15, 16 and so on.

Among

thousands

of

organic

ligands,

4,5-imidazoledicarboxylic

acid

(H3ImDC), as a widely studied rigid aromatic ligand which owns two N-O-chelating parts with an approximately angle of 144o (directed by the metal–N coordination), has demonstrated its superior ability to build MOF materials and successfully targeted to synthesize series of zeolite-like metal-organic frameworks (ZMOFs).17-22 In recent reports, with the effective modification of H3ImDC ligand on 2-position resulted in the functionalization of materials.23-25 However, unlike zeolite-like imidazole frameworks (ZIFs), 3 ACS Paragon Plus Environment


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simply functionalization cannot bring about structural varieties.26-28 Therefore, introduction of another rigid coordination moiety in 2-position may be able to bring about interesting structural changes. Accordingly, we opt to modify isophthalate-type ligands, which are well known for construct porous MOFs,29 to the 2-position. Different from traditional tetracarboxylic acid ligands, this ligand is likely to bring about different structural variations due to the different coordination modes and symmetries.

In addition to different types of ligands, the structural changes caused by metal nodes are also very common. Generally speaking, there are three factors that can cause structural differences due to metal nodes. First is the different metal source. Elements located in different cycles and groups often have different coordination numbers and patterns which fundamentally lead to rich and varied MOF materials.30-32 Secondly, different multinuclear metal nodes can bring different connection numbers.32 For example, through adjusting the reaction solvent system, different building units (mononuclear, trinuclear) and structural topologies can be exhibited with the same indium metal source and same tetracarboxylate ligand.33 Finally, the cis-trans isomerism, an important phenomenon in coordination chemistry, can also lead to remarkable structural changes.34-36 However, so far, most reported cis-trans isomerism is the ligand isomerism, the pure cis-trans isomerism of mononuclear metal node in MOF materials is rarely reported.


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In

this

regard,

a

new

tetracarboxylic

2-(3,5-dicarboxyphenyl)-1H-imidazole-4,5-dicarboxylic

acid acid

ligands,

(H5DpImDC),

which combines 4,5-imidazoledicarboxylic acid with isophthalic acid, has been designed and synthesized (Scheme 1). The assembly of H5DpImDC and Zn(II) or

Co(II)

ions

forms

two

novel

[Zn5(DpImDC)2(DMF)4(H2O)3]·H2O·DMF

porous

MOFs,

(JLU-MOF48)

named and

[Co5(DpImDC)2(DMF)4(H2O)6]·DMF (JLU-MOF49). The structures and connections of these two materials are similar, but due to the mononuclear cis-trans isomerism, there is a significant difference in symmetry. In addition, JLU-MOF48 exhibits remarkable luminescent properties and owns excellent abilities for detecting nitroaromatic explosives.

Scheme 1. Synthetic route to the ligand of H5DpImDC.

EXPERIMENTAL SECTION

Materials and methods. All chemicals were obtained from commercial sources and used without further purification. Powder X-ray diffraction (PXRD) 5 ACS Paragon Plus Environment


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data were collected on a Rigaku D/max-2550 diffractometer with Cu-Kα radiation (λ = 1.5418 Å). The thermal gravimetric analyses (TGA) were performed on a TGA Q500 thermogravimetric analyzer used in air with a heating rate of 10

o

C min-1. Luminescent spectra were collected on a

Fluoromax-4 spectrophotometer. Nuclear magnetic resonance (NMR) spectra were recorded on a Varian 300 MHz NMR spectrometer. Elemental analyses (C, H, and N) were collected by a vario MICRO (Elementar, Germany).

Synthesis of 2-(3,5-dicarboxyphenyl)-1H-imidazole-4,5-dicarboxylic acid (H5DpImDC). 5-(1H-benzo[d]imidazol-2-yl)isophthalic acid (10 g, 35.5 mmol) was added in a 500 mL 3-neck round bottom flask. Then, concentrated sulfuric acid (120 mL) was added. With constant stirring, hydrogen peroxide (75 mL) was added slowly to the mixture and kept the solution temperature between 100-110 oC. Then, the solution was heated to 140 oC and refluxed for 2 h. The hot solution was added to 600 mL ice water and kept in 4 oC refrigerator overnight. Then filtered, to result in H5DpImDC as a light yellow solid (6.4 g, 57%). 1H NMR (300 MHz, DMSO-d6) δ (ppm): 9.05 (d, J = 1.5 Hz, 2H), 8.56 (t, J = 3.3 Hz, 1H) (Figure S1).

Synthesis of JLU-MOF48. A solid mixture of H5DpImDC (0.005 g, 0.016 mmol), ZnSO4·7H2O (0.015 g, 0.052 mmol), DMF (1 mL) and H2O (0.5 mL) were sealed in a 20 mL vial and then heated at 85 oC for 24 h. Colourless block crystals were collected and washed with DMF and then dried in air (81% yield 6 ACS Paragon Plus Environment

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based on ZnSO4·7H2O). Elemental analysis (wt %) for JLU-MOF48: C, 35.28; H, 3.513; N, 9.03. Found: C, 35.50; H, 3.489; N, 9.15.

Synthesis of JLU-MOF49. A solid mixture of H5DpImDC (0.005 g, 0.016 mmol), CoSO4·7H2O (0.015 g, 0.053 mmol), DMF (1 mL) and H2O (0.8 mL) were sealed in a 20 mL vial and then heated at 85 oC for 24 h. Red block crystals were collected and washed with DMF and then dried in air (78% yield based on CoSO4·7H2O). Elemental analysis (wt %) for JLU-MOF49: C, 35.21; H, 3.820; N, 9.01. Found: C, 35.57; H, 3.882; N, 8.97.

Luminescence measurements. All the experiments were performed in room temperature. For ligand luminescence quenching experiment, 1 mg ligand was dissolved in 3 mL DMF, with gradually adding a certain concentration of nitroaromatic solution. For crystal luminescence quenching experiment, 1 mg well ground JLU-MOF48 was fully dispersed in 3 mL DMF with gradually adding a certain concentration of nitroaromatic solution. To maintain homogeneity, the suspension needed to be fully stirred after each addition and to be tested as soon as possible. In order to analyze the quenching efficiency, Stern−Volmer (SV) equation: (I0/I) = 1 + Ksv[C], in which Ksv is the quenching constant (M-1), [C] is the concentration of the nitroaromatic solution (M), I0 is the original luminescent intensity in absence of analytes, I is the luminescent intensity with molar concentration [A] of analytes, has been applied to the low concentrations. 7 ACS Paragon Plus Environment


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X-ray crystallography. Crystallographic data for the two compounds were collected

on

a

Bruker

Apex

II

CCD

diffractometer

using

graphite-monochromated Mo-Kα (λ = 0.71073 Å) radiation at room temperature. The structures of these two compounds were solved by direct methods and refined by full-matrix least-squares on F2 using SHELXL-2014.37 All the metal atoms were located first, and then the oxygen, carbon and nitrogen atoms of the compounds were subsequently found in difference Fourier maps. The hydrogen atoms of the ligand were placed geometrically. All non-hydrogen atoms were refined anisotropically. For there were lots of disordered solvent molecules in the structure, the PLATON/SQUEEZE was applied to remove their diffraction contribution.38 The final formulas of JLU-MOF48 and JLU-MOF49 were derived from crystallographic data combined with elemental and TGA analysis data. Thus, there occurred “Alert level A” about “check chemical formula weight” in the “checkCIF/PLATON report” files for two compounds. The detailed crystallographic data is listed in Table 1. Thermal ellipsoid (30%) plot of the hydrogen bonded frameworks are shown in Figure S2 and S3. Selected bond lengths and angles for the two compounds are listed in Table S1-2, respectively. Topology information for the two compounds was calculated by ToposPro.39

Table 1. Crystal Data and Structure Refinement for JLU-MOF48 and JLU-MOF49.


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Compound Formula Mw Temp (K) Wavelength (Å) Crystal system Space group a (Å) b (Å) c (Å) α (o) β (o) γ (o) V (Å3) Z, DC (Mg/m3) F(000) θ range (deg) reflns collected/unique Rint data/restraints/params GOF on F2 R1, wR2 (I>2σ(I)) R1, wR2 (all data)

JLU-MOF48 Zn5C41H49O25N9 1394.74 296(2) 0.71073 Monoclinic C2/c 29.725(6) 11.918(2) 20.677(4) 90 134.015(8) 90 5268.1(18) 4, 1.759 2352 1.956 - 25.164 16452 / 4688 0.0494 4688 / 61 / 334 1.269 0.0646, 0.1875 0.0706, 0.1909

JLU-MOF49 Co5C41H53O27N9 1398.57 296(2) 0.71073 Orthorhombic Fdd2 28.481(4) 30.215(4) 11.7852(14) 90 90 90 10142(2) 8, 1.832 4264 1.965 - 25.146 15179 / 4488 0.0391 4488 / 29 / 297 0.616 0.0351, 0.1073 0.0370, 0.1107

RESULTS AND DISCUSSION

Structure description

The

X-ray

crystallographic

analysis

reveals

that

JLU-MOF48

and

JLU-MOF49 have similar structures and connections, but with significant differences in symmetry. JLU-MOF48 crystallizes in the monoclinic crystal system with the space group of C2/c. In each asymmetric unit, there exists two and a half independent Zn(II) ion, one organic DpImDC5- anion, one DMF molecule, and two and a half coordinated H2O molecules (Figure S2). As 9 ACS Paragon Plus Environment


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shown in Figure 1 and Figure S4, from the perspective of metals, each binuclear Zn(II) is connected to four different H5DpImDC ligands and two guest DMF molecules, which can be regarded as a 4-connected node. Each mononuclear Zn(II) is connected to two different H5DpImDC ligands and two O atoms from guest molecules. From the perspective of the ligands, each ligand is connected to four different binuclear Zn(II) and one mononuclear Zn(II), which can be regarded as a (3, 4) connected node. Therefore, JLU-MOF48 adopts a new (3, 4, 4) connected topology with a Schläfli symbol of {62.8}{64.82}{65.10} (Figure S4 and S5).

JLU-MOF49 crystallizes in a higher crystal system of orthorhombic with the space group of Fdd2. In each asymmetric unit of JLU-MOF49, there exists two and a half independent Co(II) ion, one organic DpImDC5- anion and five coordinated H2O molecules (Figure S3). The most significant difference between JLU-MOF48 and JLU-MOF49 lies in the coordination mode of mononuclear metal node (Figure S6). In JLU-MOF48, mononuclear Zn(II) is trans-coordinated, the two ligands that linked the Zn(II) are almost coaxial, with only a slight twist. Whereas in JLU-MOF49, mononuclear Co(II) is cis-coordinated, the center axes of the two ligands are significantly offset. Overall, such difference didn’t fundamentally change the whole connection patterns, pore space and even the topology. However, due to the subtle differences in coordination angle, they form completely different crystal


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systems. JLU-MOF49 also adopts a new (3, 4, 4) connected topology with a Schläfli symbol of {62.8}{64.82}{65.10} (Figure S7 and S8).

Figure 1. (Middle) The ligand is simplified as a (3, 4) connected node. (Left) From a trans-coordinated mononuclear Zn(II) to form a 3D framework

JLU-MOF48 and its structural models from a viewpoint from [0 1 0] direction. (Right) From a cis-coordinated mononuclear Co(II) to form a 3D framework

JLU-MOF49 and its structural models from a viewpoint from [0 1 0] direction. (For clarity, disordered atoms were simplified and H atoms on ligands are omitted) 11 ACS Paragon Plus Environment


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Through comparing experimental PXRD patterns with the simulated one from single crystal data, the crystalline phase purity of these two materials can be confirmed (Figure S9 and S10). Furthermore, several common organic solvents, including ethanol, acetonitrile, acetone, dichloromethane and trichloromethane, have been chosen to investigate their stabilities. As shown in Figure S11,

JLU-MOF49 was stable in all tested solvents, but JLU-MOF48 was relatively unstable in dichloromethane and trichloromethane. TGA of JLU-MOF48 and

JLU-MOF49 were used to explore their thermal stabilities (Figure S12 and S13). JLU-MOF48 was observed a total weight loss of 9.5% before 150 oC, corresponding to the loss of coordinated H2O, guest H2O and guest DMF, then a total weight loss of 17.0% between 150-334 oC was corresponding to the loss of coordinated DMF, and then followed by a total weight loss of 46.0% before 561 oC, corresponding to the framework collapse. JLU-MOF49 was observed a total weight loss of 13.7% before 190

o

C, corresponding to the loss of

coordinated H2O and guest DMF, then a total weight loss of 20.1% between 190-372 oC was corresponding to the loss of coordinated DMF, and then followed by a total weight loss of 41.8% before 473 oC, corresponding to the framework collapse. Both of the two compounds exhibit relatively high thermal stability.

Property characterization


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Considering the strong π-conjugated effect of organic ligand and Zn(II) was a d10 metal ion, the fluorescent properties of JLU-MOF48 were investigated.40 As shown in Figure 2(a), the H5DpImDC ligand exhibits emission at 418 nm upon excitation at 375 nm in DMF. However, the emission peak center of

JLU-MOF48 dispersed in DMF is at 366 nm (Figure 2(b)), which displays a large blue shifts of 52 nm compared to H5DpImDC, suggesting that the luminescence emission of JLU-MOF48 may be affected by the metal nodes and ligands together. These results mean that JLU-MOF48 may be a good fluorescence sensing material candidate.

Figure 2. Excitation (dot lines) and emission (solid lines) spectra of free H5DImDC ligand dissolved in DMF (a) and powder crystal JLU-MOF48 sample dispersed in DMF (b). The emission spectra (c) and SV plot (d) of

JLU-MOF48 by gradual addition of NB in DMF (35 mM). 13 ACS Paragon Plus Environment


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As is well known to all, nitroaromatic explosives are electron deficient conjugated and can leading to the fluorescence quenching in a porous luminescent MOF due to the electron or energy transfer.1 Thus, one of the most basic nitroaromatics, nitrobenzene (NB), has been selected for research. As we expected, with the continuous addition of NB solution, fluorescent intensity decreases rapidly (Figure 2c). It decreased by 10.1% at 0.14 mM and 94.8% at 4.12 mM, respectively. As shown in Figure 2d, the SV curves of NB obviously deviate from linearity and the slope gradually decreased at high concentrations. Such phenomena can be contributed to self-absorption or an energy-transfer process.3 However, at low concentrations, the SV plots of NB is nearly linear (R2 = 0.9921) (Figure 2d insert and Figure S14). The calculated Ksv value of NB is 9.1×102 M-1, which shows that JLU-MOF48 indeed has potential for the detection of nitroaromatics.

Therefore, several nitroaromatics have been selected for further research including 4-nitrotoluene (4-NT), 2,4-dinitrotoluene (2,4-DNT), 4-nitrophenol (4-NP), 2,4-dinitrophenol (2,4-DNP) and 2,4,6-trinitrophenol (TNP). As shown in Figure 3 and Figure 4, the fluorescent intensity decreased by 27.3% at 0.14 mM and 97.8% at 2.19 mM for 4-NT solutions, 21.9% at 0.14 mM and 98.1% at 2.69 mM for 2,4-DNT solutions, 42.3% at 0.032 mM and 87.9% at 0.14 mM for 4-NP solutions, 50.6% at 0.032 mM and 91.2% at 0.14 mM for 2,4-DNP solutions and 61.2% at 0.035 mM and 95.7% at 0.14 mM for TNP solutions, respectively. The calculated Ksv values are 3.1×103 M-1 for 4-NT, 2.4×103 M-1 14 ACS Paragon Plus Environment

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for 2,4-DNT, 7.3×104 M-1 for 4-NP, 8.7×104 M-1 for 2,4-DNP and 1.0×105 M-1 for TNP (Figure S15-S19). As can be seen from the above results, the quenching

efficiencies

follow

the

order

of

TNP>2,4-DNP>4-NP>4-NT>2,4-DNT>NB and indicates that TNP is detected most effectively (Figure 5). Furthermore, JLU-MOF48 exhibited a very low detection limit towards TNP (0.25 ppm), which is lower than many reported MOFs (Figure S20 and Table S3). This is mainly due to TNP has the lowest LUMO energy among all the above nitroaromatics.1 It is for this reason that the TNP has become the strongest electron acceptor in the excited state. It is noteworthy that to the best of our knowledge, the outstanding detecting efficiency for TNP is among the highest values of MOFs (Table S3).

Figure 3. The emission spectra and SV plot of JLU-MOF48 by gradual addition of 4-NT (a, b) and 2,4-DNT (c, d) in DMF (35 mM). 15 ACS Paragon Plus Environment


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Figure 4. The emission spectra and SV plot of JLU-MOF48 by gradual addition of 4-NP (a, b), 2,4-DNP (c, d) and TNP (e, f) in DMF (1 mM).


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Figure 5. Fluorescence quenching of JLU-MOF48 by different analytes at room temperature.

In order to study the detection difference between pure organic ligands and porous MOF structures, we further examined the sensitivity of H5DpImDC ligand towards the above nitroaromatics in DMF. As shown in Figure S21-26, the KSV values of H5DpImDC ligand are 1.4×102 M-1 for NB, 1.5×102 M-1 for 4-NT, 2.2×102 M-1 for 2,4-DNT, 2.3×103 M-1 for 4-NP, 2.2×103 M-1 for 2,4-DNP and 5.8×104 M-1 for TNP. The quenching efficiencies follow the order of TNP>4-NP>2,4-DNP>2,4-DNT>4-NT>NB. The outcome shows that the porous crystalline JLU-MOF48 is more efficient than H5DpImDC ligand for the detection of those nitroaromatics, which may be attributed to the existence of channels to promote the host-guest interplay. This proves that the crystalline porous MOF materials have great advantages in detection of nitroaromatics.

CONCLUSION

In summary, two novel porous MOFs constructed by a ligand combined 4,5-imidazoledicarboxylic acid with isophthalic acid have been solvothermally synthesized. Two compounds possess similar structures and same topologies. Due to the cis-trans isomerism in mononuclear metal nodes, significant differences occurred in two materials’ symmetries. JLU-MOF48 exhibits remarkable detecting ability towards TNP. Furthermore, JLU-MOF48 can also detect other nitroaromatic explosives efficiently. Finally, this burgeoning 17 ACS Paragon Plus Environment


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crystalline material may be a promising candidate for detecting nitroaromatic explosives.

ASSOCIATED CONTENT

Supporting Information. Structure information (CCDC 1583714 and 1583715), PXRD, TGA, emission spectra of JLU-MOF48 in low concentration range, fluorescent properties of H5DpImDC ligand, detection limit. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *(L. Z.) Email: [email protected]; *(Y. L.) Fax: +86-431-85168624. E-mail: [email protected]. Notes The authors declare no competing financial interests. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (No. 21771078, 21621001, and 21671074) and the 111 Project (B17020). REFERENCES


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For Table of Contents Use Only Two Metal-Organic Frameworks with Structural Varieties Derived from Cis-Trans Isomerism Nodes and Effective Detection of Nitroaromatic Explosives Jiantang Li, Xiaolong Luo, Yue Zhou, Lirong Zhang,* Qisheng Huo and Yunling Liu*

JLU-MOF48 and JLU-MOF49 have been constructed by using a ligand combined 4,5-imidazoledicarboxylic acid with isophthalic acid and the structures are different in cis-trans isomerism. JLU-MOF48 exhibits remarkable luminescent properties and owns outstanding performance for detecting nitroaromatic explosives.


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