Two Lanthanide MetalâOrganic Frameworks as Remarkably Selective

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Two Lanthanide Metal-Organic Frameworks as Remarkably Selective and Sensitive Bifunctional Luminescence Sensor for Metal Ions and Small Organic Molecules Wei Yan, Chuanlei Zhang, Shu-Guang Chen, Lijuan Han, and He-Gen Zheng ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b14563 • Publication Date (Web): 21 Dec 2016 Downloaded from http://pubs.acs.org on December 22, 2016

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ACS Applied Materials & Interfaces

Two Lanthanide Metal-Organic Frameworks as Remarkably Selective and Sensitive Bifunctional Luminescence Sensor for Metal Ions and Small Organic Molecules Wei Yan, Chuanlei Zhang, Shuguang Chen, Lijuan Han and Hegen Zheng* State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, P. R. China KEYWORDS: Ln-MOFs, uncoordinated site, fluorescence detection, sensor materials, nitromethane

ABSTRACT: Two lanthanide metal-organic frameworks (Ln-MOFs) with similar structures have been synthesized through objective synthesis. Two compounds are both two-fold interpenetrating 3D frameworks. Topological analyses reveal that complexes 1 and 2 are 6-connected pcu net. In addition, both the two structures were embedded in uncoordinated nitrogen atoms. As the uncoordinated pyridine groups can be used as functional groups, we tested their sensing ability towards metal ions and small organic molecules. To our delight, fluorescence measurements

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show the two complexes can selectively and sensitively detect for Fe3+ ion and nitromethane, which suggests that the two Ln-MOFs are promising bifunctional luminescence sensor materials with sensing metal ions and small organic molecules.

INTRODUCTION Over the past decades, metal-organic frameworks have aroused great attentions due to their potential application in sensitive and selective detection for environmental contaminants,1-4 which can protect human health and the environment from pollution damage. In the methods reported in the literatures, luminescence-based methods have been widely studied because of their significant advantages, namely, high selectivity, high sensibility, short response time, easy to operate and visualization. Therefore, combining the advantages of the MOFs and luminescence sensors is a hot research topic. Among all luminescence MOFs, lanthanide metalorganic frameworks (Ln-MOFs) have more significant advantages and characteristics than the transition-metal-organic frameworks, i.e., high optical purity, large Stokes shift value, high quantum yields, sharp emission peaks, visible color change identified by naked eyes, long luminescence lifetimes, which arise from f-f transitions via an “antenna effect”.5-8 As the lanthanide ions and some organic linkers can be easily incorporated into Ln-MOFs by selfassembly, which provide a charming platform to achieve the diverse lanthanide-centered luminescence, thus, Ln-MOFs become a research focus for majority of scientists.9-12 The design and synthesis of metal ion sensing probes have attracted much attention of researchers on account of the significant role of metal ions in environmental and ecological system. Among them, Fe3+ is one of the most important kinds of metal ions. Besides, Fe3+ is also


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a ubiquitous metal in biochemical processes such as cell metabolism, electron transfer enzyme catalysis, oxygen transport and synthesis of DNA and RNA. The excess or deficiency of iron ion can result in the physical illness like anemia, mental decline, arthritis, diabetes, cancer and etc.1315

On the other hand, with the rapid development of industry and the social activities of human

beings, a great amount of toxic organic small molecules and heavy metal ions are released into the environment for human survival which have caused a lot of adverse effects to the environment and the health of human being.16-18 In general, the nature of organic ligands and metal ions can significantly affect properties of the MOFs-based materials. So, we choose two organic ligands H2L and BPDC (H2L = 2,5di(pyridin-4-yl)terephthalic acid, BPDC = biphenyl-4,4'-dicarboxylic acid) (Scheme S1) and two lanthanide ions to construct MOFs for a number of reasons: (1) The rigidity of the two ligands can help to construct stable networks; (2) The uncoordinated pyridine groups can be used as functional groups to detect metal ions and small organic molecules; (3) The characteristic emission peaks and unique color of the lanthanide ions can provide practical optical signal. In our work, we exhibit two new Ln-MOFs {[Eu(L)(BPDC)1/2(NO3)]·H3O}n (1) and {[Tb(L)(BPDC)1/2(NO3)]·H3O}n (2) based on H2L and BPDC Ligand. The two crystals are isomorphous and they are 2-fold interpenetrated 3D networks with lewis basic pyridyl sites. Fluorescence tests of complexes 1 and 2 show highly sensitive sensing of Fe3+ ion and nitromethane. RESULTS AND DISCUSSION The experimental section has been listed in the Supporting Information. The detailed information of complexes 1-2 is summarized in Table S1 and S2.


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Single crystal X-ray diffraction study reveals that two crystals are similar structures and crystallize in the monoclinic crystal system with P2(1)/n space group. Therefore, only structure of 1 is described in detail. As shown in Figure S1 (a), each asymmetric unit of 1 contains one Eu(III) metal center, one L ligand, half a BPDC ligand and one lattice water molecule. The carboxylate groups of L ligand coordinate to Eu(III) ions while the pyridyl groups remain uncoordinated. The carboxylate groups of L ligand shows two bonding modes: a chelating mode and a bridging-chelating mode (Figure S1 (c), left). One of the carboxylate groups of L ligand adopts chelating and bridging modes to link two Eu3+ ions, the other one acts as a chelating mode. In addition, the carboxylate groups of BPDC ligand appears a simple chelating mode (Figure S1 (c), right). Each Eu(III) ion is 9-coordinated and bonds to two bridging-chelating carboxylate, one chelate carboxylate, two bridging BPDC2- anion and one NO3- ion. Pairs of Eu(III) cations are connected by four L ligands to generate a dinuclear secondary building unit (SBU) with a Eu···Eu separation of 3.928(4) Å (Figure 1(a)). These SBUs are further bridged through L ligands into a 1D layer. Then BPDC ligands connect the layers to form a 3D network (Figure 1(b)). The two identical networks aforementioned appeared in the same crystal lattice of compound 1, thus resulted in a 2-fold interpenetrated pcu framework (Figure S1(b)). (a)

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Figure 1 (a) Coordination environment of Eu(III) cations in 1. (b) The three-dimensional framework of 1.

Thermal Stabilities and PXRD. To check the purity of crystal structures, the PXRD experiments for 1 and 2 were carried out. As shown in Figure S2-S3, the as-synthesized samples and simulated patterns are in well agreement with each other. To further investigate the stability of complexes 1-2, thermal gravimetric analysis (TGA) of compounds 1-2 were studied in detail (Figure S7). The weight loss of 2.75% (calcd 2.68%) for 1 and 2.80% (calcd 2.66%) for 2 can be regarded as the loss of one water molecule between 162 °C and 268 °C. After 424 °C, the rapid weight loss can be considered as the collapse of the skeleton of 1, while the framework of complex 2 starts to decompose until 377 °C. Luminescent Properties. The luminescent properties of complexes 1 and 2 were also investigated. As shown in Figure S8, the luminescence spectrum of 1 reveals characteristic photoluminescence properties with the fluorescence peaks at 594, 618 and 699 nm, which are contributed from the 5D0 → 7F1, 5D0 → 7F2, and 5D0 → 7F4 transitions of Eu3+ ion, respectively (excitation wavelength: 338 nm).19 For complex 2, the evident typical transitions of the Tb3+ ion can be observed at 490, 545, 587, and 622 nm, which could be attributed to the 5D4 → 7F6, 5D4 → 7F5, 5D4 → 7F4, and 5D4 → 7F3 transitions (excitation wavelength: 327 nm), separately.20 Besides, we tested their emission decay lifetimes. The luminescent decay curves were fitted with a double-exponential decay function (Figure S11 - S12). The emission decay lifetimes for 1 are τ1 = 32.88 µs, τ2 = 112. 29 µs; for complex 2, τ1 = 709.02 µs, τ2 = 1201.01 µs.


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Figure 2 (a) The photoluminescence spectra of 1 introduced into various cations. (b) The photoluminescence spectra of 2 introduced into various cations. (c) Photographs showing color changes after adding metal ions under 365 nm ultraviolet light (up: MOF-1; down: MOF-2). (d)The luminescence intensities after introduced into various cations (red: the 5D0 → 7F2 transition intensity of 1, blue: the 5D4 → 7F5 transition intensity of 2).

As the pyridyl groups of 1 are uncoordinated, we investigate their sensing ability for metal cations and small organic molecules. The results of fluorescence sensing measurements show that 1 has a good selectively sensing for iron ion and nitromethane. To further confirm the considerable role of pyridine group in the detection, we have synthesized compound 2, which has the similar structure with 1. To our delight, 2 displayed the same quenching effect for iron ion and nitromethane. The results were discussed in detail as follows. Detection of Metal Ions. The compound 1 was taken as an example to discuss. Equal volumes of different DMF solutions containing 10−2 M of M(NO3)x (M = Na+, K+, Cu2+, Fe3+, Al3+, Mg2+,


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Cr3+, Zn2+, Co2+) were added in the suspension of crystals. Obviously, only Fe3+ ions show an excellent quenching effect on the luminescence of complex 1 (Figure 2a and Figure S13). Furthermore, the process of detection is accompanied by visible changes in colour. As we can see from Figure 2c (up), under the irradiation of 338nm, the pink solution significantly changed a lot after the addition of iron ions, which makes its simple to distinguish by the naked eye. Compound 2 demonstrated the similar quenching effect with 1 (Figure 2b and Figure 2c (down) and Figure S14). Figure 2d shows the photoluminescence intensity decreased to 7.03% for 1 and 9.40% for 2, respectively. Quantitatively, the photoluminescence quenching effect can be explained by the Stern-Volmer (SV) equation: I0/I = 1 + Ksv[M], where the Ksv is the quenching effect coefficient (M-1), [M] is the molar concentration of the metal ions, I0 and I are the luminescence intensities before and after incorporation of metal ions, respectively. As we are expected, the reduction of fluorescence intensity is related to the concentration of metal ions. The Stern-Volmer curves for Fe(III) ion are nearly linear at low concentrations (R2 = 0.9986 for 1 and 0.9972 for 2) (Figure 3b and Figure 3d). However, with the increase of concentration, the curves deviate from the linearity which can be explained by an energy-transfer process or self-absorption.21-25 Ksv were obtained directly from the experimental database at low concentrations (The insets of Figure 3b and Figure 3d). The experimental results show complexes 1 and 2 have relatively high Ksv of values with Fe3+, at 5.16 × 104 M-1 for 1 and 4.30 × 104 M-1 for 2, respectively, which are comparable to those of known Ln-MOFs (Table S4).26-30


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Figure 3 (a) The photoluminescence spectra and (b) SV curve for 1 by gradual addition of 1 mM Fe3+ ions in DMF. (c) The photoluminescence spectra and (d) SV curve for 2 by gradual addition of 1 mM Fe3+ ions in DMF. The insets demonstrate the quenching linearity relationship at low concentrations of Fe3+ ion.

Detection of Small Organic molecules. Organic solvents are commonly used in commercial production. However, they have adverse impact on the human health and environment. As a kind of novel sensing material, luminescent Ln-MOFs have been widely used in the detection of small organic molecules in environment via the notable changes of luminescent signals caused by those pollutants. On the basis of the above consideration, further fluorescence sensing experiment was carried out to explore the effect of guest molecules on compounds. Several common organic solvents were selected to investigated, such as acetone, dichloromethane


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(CH2Cl2), methanol (MeOH), ethanol (EtOH), N,N-dimethylformamide (DMF), N,Ndimethylacetamide (DMA), N-methyl-2-pyrrolidone (NMP), acetonitrile (CH3CN), 1,4-dioxane, dimethyl sulfoxide (DMSO), trichloromethane (CHCl3) and nitromethane (NM). Delightedly, the fluorescence intensities of two complexes are largely dependent on the solvent species, especially for nitromethane, which reveals intense quenching effect (Figure 4a and Figure 4b). 30 µL different organic solvents mentioned above were added to the suspension of crystal samples. It can be clearly seen that the fluorescence intensity of the compounds with the addition of nitromethane were almost fully quenched (Figure S15 - S16). The quenching proportions reached 98.35% for 1, 99.34% for 2 (Figure 4c). (a)

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Figure 4 (a) The photoluminescence spectra of 1 introduced into various pure solvents. (b) The photoluminescence spectra of 2 introduced into various pure solvents. (c) The luminescence intensities after introduced into various pure solvents (red: the 5D0 → 7F2transition intensity of 1, blue: the 5D4 → 7F5 transition intensity of 2).

The mechanism of luminescence quenching. To explain the high selectivity of the two complexes towards Fe3+ ion and NM, we investigated their quenching mechanism. Firstly, the quenching mechanism of iron ion for MOFs is discussed. The luminescence of Ln-MOFs arising from the “antenna effect” consisted of the following three steps: the light is absorbed by the organic ligands around the lanthanide ions, and then energy is transferred from organic ligands to lanthanide ions, the luminescence was generated from lanthanide ions eventually.31 Therefore, the quenching mechanism caused by the addition of metal ions might be explained by ligand to metal charge transfer (LMCT). To verify our speculation, 5 mg of compounds 1 and 2 were dispersed in 3 mL of Fe3+ solution with a concentration of 0.75 µM. After immersion for 12 h, respectively, the concentrations of Fe3+ were detected for ICP determination. As shown in Table S3, the Fe3+ concentrations in the filtrate solution obviously decreased which indicates that there is a weak interaction between MOFs and Fe3+. From the point of view of crystal structures, two pyridyl groups of H2L ligand are uncoordinated and provide binding sites for metal ions. The ions having a saturated electron configuration such as K+, Mg2+, Na+, Zn2+, Al3+ basically show no quenching effect, however, Ni2+, Co2+, Cr3+, Cu2+ with different electron configurations, appears different quenching effects for the luminescence intensity of the compounds. The remarkable differences of quenching effect mainly ascribe to the binding ability of pyridine N atoms in H2L toward metal ions. What’s more, the relatively small ionic radius of Fe3+ leads to an easy combination of Fe3+ and pyridine N atoms.32 The interaction between pyridine N atoms and Fe3+ is expected to perturb the singlet and triplet excited states of ligands.33 There is no doubt that this will affect antenna efficiency and further decrease the energy transitions from


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ligands to lanthanide ions, leading to the luminescence quenching. To confirm this speculation, studies of N1s X-ray photoelectron spectroscopy (XPS) were tested on MOF 1 and Fe3+ @ MOF 1, MOF 2 and Fe3+ @ MOF 2. The N1s peak of pyridyl nitrogen atoms at 400.1 eV in MOF 1 is shifted to 400.9 eV after addition of Fe3+, while the N1s peak of pyridyl nitrogen atoms at 401.2 eV in MOF 2 is shifted to 402.0 eV on the addition of Fe3+ (Figure S19 – S20), which further verify the weak binding between pyridyl nitrogen atoms and Fe3+.34 Although the quenching mechanism towards solvents is still unclear, the luminescence response towards nitromethane was attributed to the effect of ligand-to-metal energy transformation (LMET), because the emission efficiency of LMET determine the luminescent intensity.33 For comparison, we studied the UV-Vis absorption spectrum of the ligands, NM, MOF 1 and MOF 2 (Figure S21). The results showed that NM in DMF solution has a better UV-Vis adsorption ability in the range at 320-400 nm than the ligands. As the excitation wavelength of MOF 1 is 338 nm (MOF 2 is 327 nm), the luminescence decrease of the MOF 1 and MOF 2 after the addition of NM can be attributed to the competition of absorption of the light source energy and the electronic interaction between the NM and H2L ligands. The NM filters the light adsorbed by H2L ligands which resulted in the decrease the probability of energy transfer from H2L ligands to lanthanide ions, the luminescent intensity of MOF 1 and MOF 2 was obviously decreased.19, 35 CONCLUSIONS In conclusion, two lanthanide metal-organic frameworks with the similar structures were designed and synthesized. Luminescence sensing measurements indicate that Ln-MOFs 1 and 2 with uncoordinated pyridine groups show highly selective and sensitive sensing for Fe3+ ion and nitromethane. Furthermore, the quenching mechanism was discussed in detail. This work provides a useful idea to design and synthesis of Ln-MOF-based sensors in a reasonable way.


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ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at http://pubs.acs.org Crystallographic data for 1 in CIF format (CIF) Crystallographic data for 2 in CIF format (CIF) Experimental details, the selected bond lengths and angles, structural drawing, IR, PXRD, TGA, ICP, photoluminescence spectra, XPS, UV-Vis(PDF).

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Notes The authors declare no competing financial interests. ACKNOWLEDGMENT This work was supported by grants from the National Natural Science Foundation of China (No. 21371092, 91022011) and National Basic Research Program of China (2010CB923303).

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Two Lanthanide Metal-Organic Frameworks as Remarkably Selective and Sensitive Bifunctional Luminescence Sensor for Metal Ions and Small Organic Molecules Wei Yan, Chuanlei Zhang, Shuguang Chen, Lijuan Han and Hegen Zheng*

Two lanthanide metal-organic frameworks with similar structures have been synthesized. Fluorescence measurements show the two complexes can selectively and sensitively detect metal ions and small organic molecules.


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Two Lanthanide MetalâOrganic Frameworks as Remarkably Selective

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Two Lanthanide MetalâOrganic Frameworks as Remarkably Selective