A pillar-layer MOF used as a luminescent probe for detecting small molecules acetone

    A pillar-layer MOF used as a luminescent probe for detecting small molecules acetone Bao-Li Li, Hai-Ning Wang, Liang Zhao, Guang-Zhe Li, Zhong-Min Su PII: DOI: Reference:

S1387-7003(15)30174-X doi: 10.1016/j.inoche.2015.12.019 INOCHE 6201

To appear in:

Inorganic Chemistry Communications

Received date: Revised date: Accepted date:

26 October 2015 4 December 2015 29 December 2015

Please cite this article as: Bao-Li Li, Hai-Ning Wang, Liang Zhao, Guang-Zhe Li, ZhongMin Su, A pillar-layer MOF used as a luminescent probe for detecting small molecules acetone, Inorganic Chemistry Communications (2016), doi: 10.1016/j.inoche.2015.12.019

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ACCEPTED MANUSCRIPT A pillar-layer MOF used as a luminescent probe for detecting small molecules acetone

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Bao-Li Lia, Hai-Ning Wangb, Liang Zhaoa, Guang-Zhe Lia, Zhong-Min Sua,*

Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal

College of Chemical Engineering, Shandong University of Technology, Zibo,

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University, Changchun 130024, Jilin (P.R. China)

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Shandong, 255049, China.

* Corresponding author. Tel.: +86-431-85099108. E-mail address: [email protected].

ACCEPTED MANUSCRIPT Abstract The reactions of 4,4-bipyridine and 5-Hydroxyisophthalic acid with Zn(NO3)2·3H2O

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in N,N’-dimethylacetamide lead to the formation of [Zn(5-hip)(bpy)]·2DMA (1).

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Compound 1 possesses a non-interpenetrating pillar-layer framework with 1D

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rectangular-shape channels. The experimental results show that the luminescent intensity of 1 highly depends on small solvent molecules, particularly CH3OH and

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acetone. Compound 1 can be used as a luminescent probe to detect small molecules

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acetone.

Keywords: metal–organic frameworks, luminescence, sensing

ACCEPTED MANUSCRIPT Recognition and sensing of small molecules have drawn more and more interest because of their important roles in environmental systems [1]. The common recognition reports are putting a guest molecule into the cavity of a host framework.

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To serve as a useful sensor, the host should bind to the guest in preference to all competing species and it must register the binding event in a measurable form. In

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addition, the host molecules are also chemical and thermal stability. The required features make porous Metal–Organic Frameworks (MOFs) an attractive choice for molecular sensing [2].

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Over the past few years, MOFs constructed via the self-assembly of metal cations or metal clusters and organic ligands, play an important role in the field of materials

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for their various topological architectures, tunable pore sizes, and robust thermal stability [3]. Given these charming features, they possess potential applications in gas

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storage [4], catalysis [5], proton conducting [6], and sensing [1]. The organic ligands

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usually possess a conjugated π-electron system, thus making MOFs bind small molecules [7]. Furthermore, MOFs display a wide range of luminescent properties

and

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due to the multiple characteristic of their structures. A popular approach is to design synthesize

porous

lanthanoid-organic

frameworks.

The

reported

lanthanoid-derived MOFs for sensing applications have highlighted the significance

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of luminescent MOFs, such as the rapid and selective sensing of nitroaromatic compounds research by Sun groups [8]. Meanwhile, a variety of transition metal–organic frameworks used for molecular sensing have also been reported, for example, a molecular recognition platform for recognizing aromatic amine [9]. Inspired by the pioneering achievements, the synthesis of the extended MOFs attracts our attention. Fortunately, a pillar-layer framework (1) based on 5-hip and bpy has been achieved through numbers of previous experiments. Herein the synthesis, crystal growth and structural characterization of this framework will be presented and discussed. Furthermore, the sensing property of 1 has also been investigated.

Figure 1. (a) The asymmetric unit of 1; (b) The coordination environment of the Zn(II)

ACCEPTED MANUSCRIPT center; (c) The 2D layers consisted of 5-hip and Zn(II); (d) The 2D layers pillared by the bpy ligand generate a 3D pillar-layer framework (c-axis). The hydrogen atoms are

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omitted for clarity.

Single-crystal X-ray analysis reveals that compound 1 crystallizes in the

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monoclinic system with space group P21/c [10]. The asymmetric unit consists of one 5-hip ligand, one bpy ligand, and one zinc ion (Figure 1a). As shown in Figure 1b, the Zn1 has a slightly distorted triangular bipyramid geometry coordinated by three

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oxygen atoms from three 5-hip ligands and two nitrogen atoms from two bpy ligands. The average Zn–O bond length is 1.979 Å. One carboxylate group of 5-hip

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ligand bridges two ZnII centers in μ2-η1: η1 mode, and the other coordinates to another ZnII center. Thus, a 32-atom macrometallocycle generates by four zinc ions and four

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5-hip ligands, with dimensions 9.5 Å × 7.9 Å (Figure 1c). Each macrometallocycle

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sharing edge to these adjacent ones gives birth to a 2D sheet (Figure 1c). Therefore, the adjacent sheets are mutually interlinked via the bpy ligand with the distance

importantly,

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approximately 11.45 Å and extend to a 3D pillar layer framework (Figure 1d). this

framework

exhibits

two

kinds

of

interconnected

More 1D

rectangular-shape channels, with the dimensions 5.353 ×11.319 Å and 5.610 ×11.446

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Å without taking van der Waals radius in consideration (Figure S1). The total potential solvent accessible volume is 1237 Å3, which is 48 % of the unit cell volume of 2587.91 Å3 as calculated by PLATON [11]. Phase purity of the bulky crystals was confirmed by the similarity between the experimental and simulated powder X-ray diffraction (PXRD) patterns (Fig. S5). The difference in reflection intensity between experimental and simulated PXRD patterns is probably due to the preferred orientation effect of the powder sample.

Figure 2. Comparison of the luminescent intensity of 1-solvent at room temperature.

Until now, many kinds of analytical techniques such as spectrophotometry, voltammetry and atomic absorption spectroscopy have been developed for detecting

ACCEPTED MANUSCRIPT small molecules. The above techniques are not wide use in the field due to limited portability, high cost, and these instruments need frequent careful maintenances. Photoluminescence-based sensors have been considered to be the most effective tool

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for detection due to their high sensitivity and affordability [12]. In recent years, recognition and sensing of small molecules through this approach have attracted more

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and more attention [13]. Compound 1 formed by d10 metal ions Zn2+ and conjugated organic linkers can act as a candidate for potential luminescent materials, which inspire us to systematically explore its potential application in this field. The finely

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ground sample of 1 (3 mg) is immersed in different organic solvents (5 mL), treated by ultrasonication for 90 min, and then aged for 3 h to generate stable suspensions

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before the fluorescence study. The solvents used are methanol (CH3OH), ethanol, 1, 2-propanediol, dioxane, tetrahydrofuran (THF), N, N-dimethylformamide (DMF), N,

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N-dimethylacetamide (DMA), isopropanol, acetone and acetonitrile. Naturally, the

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luminescent properties of 1 in different solvent emulsions are measured (Figure S3). As shown in Figure 2, the PL intensity largely depends on the solvent, especially in

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the case of CH3OH, which exhibits the most obvious enhancing effects. The luminescent intensity increases remarkably in the presence of CH3OH, while the changes of the intensity in others are not obvious. Shifts in emission peaks can also be

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found when the solvent changes, and the intensity corresponding to the maximum peak decreases in the order CH3OH > dioxane > DMA > 1, 2-propanediol > ethanol > DMF > acetonitrile > isopropanol > tetrahydrofuran (THF) > Acetone. Exposure to the acetone/CH3OH mixtures gives rise to acetone concentration-dependent responses, the luminescence intensity gradually increases with increasing amounts of CH3OH (Figure S4). The relationship between concentration and intensity is given in the Figure 3. The result indicates that 1 could be a promising luminescent probe for detecting small molecules acetone. Acetone shows the most obvious quenching effect on the luminescent intensity. So, acetone is selected as a representive in order to explain the reason for the luminescence. Acetone has a wide absorption range from 307 to 360 nm [13b]. The absorbing band of acetone overlays part of the absorption band of 1-DMA, which may

ACCEPTED MANUSCRIPT lead to that energy transfer occurs between the 1-DMA and the acetone molecules. Due to the intermolecular solute-solvent interactions between 1-DMA and acetone, the energy absorbed by 1-DMA is transferred to acetone molecules, resulting in a

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decrease in the luminescent intensity.

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Figure 3. The profile of PL peak intensity vs solvent composition of the CH3OH-acetone mixture (excited at 377 nm).

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Conclusion

In summary, compound 1 possesses a non-interpenetrating pillar-layer framework,

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which can be used as a luminescent probe to detect small molecules. The experimental results show that the luminescent intensity of 1 highly depends on small

Acknowledgements

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molecules acetone. Further studies about this field are currently under way in our lab.

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This work was financially supported by the Science and Technology Development Planning of Jilin Province (Grant 20140203006GX).

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Appendix A. Supplementary material CCDC-1432881 (1) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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ACCEPTED MANUSCRIPT gamma = 90, V = 2587.9(17) Å3, Z = 4, ρcalcd = 1.476 g cm-3, final R1 = 0.0612 and wR2 = 0.1488 (Rint = 0.0945) for 4604 independent reflections [I>2σ(I)]. The intensity data were collected on a Bruker SMART APEXII CCD diffractometer

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Fig. 1

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Fig. 2

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Fig. 3

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A pillar-layer MOF used as a luminescent probe for detecting small

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molecules acetone

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Bao-Li Lia, Hai-Ning Wangb, Liang Zhaoa, Guang-Zhe Lia, Zhong-Min Sua,* a

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Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (P.R. China) b College of Chemical Engineering, Shandong University of Technology, Zibo, Shandong, 255049, China.

Graphical abstract

ACCEPTED MANUSCRIPT A pillar-layer MOF used as a luminescent probe for detecting small molecules acetone Wangb,

Liang

Zhaoa,

Guang-Zhe

Lia,

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Hai-Ning

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Bao-Li Lia, Zhong-Min Sua,* a

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Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (P.R. China) b College of Chemical Engineering, Shandong University of Technology, Zibo, Shandong, 255049, China.

Abstract

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The reactions of 4,4-bipyridine and 5-Hydroxyisophthalic acid with Zn(NO3)2·3H2O in

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N,N’-dimethylacetamide lead to the formation of [Zn(5-hip)(bpy)]·2DMA (1).

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Compound 1 can be used as a luminescent probe to detect small molecules acetone. The results show that the luminescent intensity of 1 highly depends on small

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molecules acetone. The luminescent intensity decreases gradually with the increase

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of amounts of acetone.

ACCEPTED MANUSCRIPT A pillar-layer MOF used as a luminescent probe for detecting small molecules acetone

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Bao-Li Lia, Hai-Ning Wangb, Liang Zhaoa, Guang-Zhe Lia, Zhong-Min Sua,* a

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Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin (P.R. China) b College of Chemical Engineering, Shandong University of Technology, Zibo, Shandong, 255049, China.

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Research Highlights

＞ A new metal-organic framework has been obtained and described.

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＞ It possesses a non-interpenetrating pillar-layer framework with 1D channels.

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＞ It can be used as a luminescent probe to detect small molecules acetone.

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＞ Its luminescent intensity decreases with the increase of amounts of acetone.