Two New Luminescent Cd(II)-MetalâOrganic Frameworks as

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Two New Luminescent Cd(II)-MOFs as Bi-functional Chemosensors for Detection of Cations Fe3+, Anions CrO42- and Cr2O72- in Aqueous Solution Shu-Guang Chen, Zhenzhen Shi, Ling Qin, Hai-Lang Jia, and He-Gen Zheng Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01197 • Publication Date (Web): 29 Nov 2016 Downloaded from http://pubs.acs.org on December 1, 2016

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Crystal Growth & Design

Two New Luminescent Cd(II)-MOFs as Bi-functional Chemosensors for Detection of Cations Fe3+, Anions CrO42- and Cr2O72- in Aqueous Solution Shuguang Chen, Zhenzhen Shi, Ling Qin, Hailang Jia, 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 ABSTRACT: Two new luminescent Cd(II)-MOFs, {[Cd(L)(BPDC)]•2H2O}n (1) and {[Cd(L)(SDBA)(H2O)]•0.5H2O}n

(2)

[L

=

4,4'-(2,5-bis(methylthio)-1,4-phenylene)dipyridine, H2BPDC = 4,4'-biphenyldicarboxylic acid, H2SDBA = 4,4'-sulfonyldibenzoic acid], have been solvothermally synthesized using Cd2+ ion and L ligand in the presence of auxiliary ligands, and characterized by infrared

spectroscopy,

elemental

analysis,

powder

X-ray

diffraction

and

thermogravimetry measurement. Topological analyses reveal that MOF 1 is a 6-connected 3-fold interpenetrating pcu network and MOF 2 is a new 4-connected 2-fold interpenetrating network. Fluorescence titration, cyclic and anti-interference experiments demonstrate that MOFs 1 and 2 both are excellent probes for Fe3+, CrO42- and Cr2O72-. The mechanisms of quenching are also deeply studied. 1. INTRODUCTION Over the last couple of decades, metal-organic frameworks (MOFs) have acquired enormous development not only in virtue of their multifarious structures given by luxuriant organic linkers and metal ions but also due to their significant potential value in gas storage,1-4 magnetism,5-7 catalysis,8-10 drug delivery11-12 and chemosensors.13-17 In

1 Environment ACS Paragon Plus


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recent years, luminescent MOF-based probes have attracted immense interest because of their particular preponderance such as monitor in real-time, quick response, high sensitivity etc., so numerous MOFs have been synthesized as sensors for the detection of ions, explosives and small molecules. As we all known, Fe3+ is a kind of ample trivalent metal ion for all organisms and plays a vital role in various crucial processes of electron transfer in DNA and RNA formation and biological metabolism.18 Iron shortage or nimiety both will result in various serious function condition disorders, such as skin diseases, iron deficiency anemia (IDA), agrypnia and decreased immunity. Alzheimer’s, Huntington’s, and Parkinson’s diseases also have been relevant to the abnormal distribution of the iron.19 Though Fe3+ is very important for organisms, excess Fe3+ will result in environmental pollution.20 Hexavalent chromium ion is harmful for human health because it will result in skin allergy and ulcers, coryza, lung cancer, renal failure and induce gene mutation after concentration in body. Kinds of methods have been developed to monitor these ions like ion mobility spectroscopy (IMS), inductively coupled plasma (ICP), X-ray dispersion, voltammetry, atomic absorption spectroscopy etc., some of which are limited in their characterization. Conversely fluorescent probes have acquired rapid development because they can provide simple, fast, selective, accurate, and cost-efficient real-time monitoring. So numbers of new MOFs are developed as chemsensors,21-22 but there are few MOFs as bi-functional chemosensors to detect for Fe3+, CrO42- and Cr2O72- ions.23 Therefore high sensitive sensors for detecting these ions in aqueous solution simultaneously are very important. Encouraged by above aspects and our previous works, we herein use linear L ligand and two auxiliary ligands as organic linkers with Cd2+ ion to synthesize two new luminescent MOFs 1 and 2. Single crystal X-ray diffraction analyses shows that both MOFs are 3D interpenetrating networks. Excellent fluorescent characteristic endowed by two auxochromic methylthios and Cd2+ ion have been confirmed by fluorescence spectrophotometer

at

ambient

temperature.

Fluorescence

titration,

cyclic

and

anti-interference experiments confirm that they have excellent potential in sensing for Fe3+, CrO42- and Cr2O72-. Quenching mechanisms also have been studied deeply herein.


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2. EXPERIMENT SECTION The experimental section has been listed in the Supporting Information. The detailed information of complexes 1-2 is summarized in Table S1 and S2.

3. RESULTS AND DISCUSSION 3.1. Structural Description of {[Cd(L)(BPDC)]·2H2O}n (1) Single crystal X-ray diffraction reveals that complex 1 crystallizes in the monoclinic crystal system of P21/c and its asymmetric unit contains one Cd2+, one BPDC2-, one L ligand and two lattice water molecules squeezed by PLATON. As shown in Figure 1a,

Figure 1. (a) Coordination environment of Cd2+ ion in complex 1. The hydrogen atoms are omitted for clarity. Symmetry codes: #1: x + 1, − y + 1/2, z – 1/2; #2: − x + 2, y – 1/2, – z + 3/2; #3: x + 1, y, z + 1; #4: − x + 3, – y, – z + 1. (b) 2D layer of 1. (c) A single porous 3D network of 1. (d) The 3-fold interpenetrating network of 1.



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each Cd2+ ion is six-coordinated with slightly distorted {CdN2O4} octahedral coordination geometry. Cd1 ion is coordinated by four carboxylate oxygen atoms from three different BPDC2- ligands at the equatorial positions and two nitrogen atoms from two L ligands at the axial positions with the N(1)-Cd(1)-N(2)#3 angles of 167.35(14)°. The Cd-O bond lengths are in the range from 2.227(3) Å to 2.399(4) Å and the Cd-N bond lengths are 2.337(4) Å and 2.356(4) Å. All carboxylic groups of BPDC2- ligand are deprotonated. Two BPDC2- ligands adopting bis-monodentate bridging modes link the Cd1 ion and a symmetrically related Cd1#4 ion to form a [Cd2(COO)2] dinuclear subunit (SBU) which contains eight-membered noncoplanar ring with Cd···Cd distances of 3.8698(5) Å. Such SBUs are further extended into a 2D layer (Figure 1b) by the carboxylic groups of BPDC2- ligands adopting bidentate-chelating modes. L ligands adopting bridge modes are pillared these 2D layers, resulting in the formation of a single 3D porous network (Figure 1c). From a topological perspective, the binuclear SBU could be regarded as a 6-connected node. Thus, the single 3D network can be described as a 6-connected pcu topology with the point symbol of {412.63}. In order to minimize the presence of cavities to stabilize the structure during the assembly process, two other identical networks are filled in the voids yielding a 3-fold interpenetrating network, as shown in the Figure 1d. The interpenetration can be classified as type Class Ia, Z = 3 (Zt = 3; Zn = 1).24

3.2. Structural Description of {[Cd(L)(SDBA)(H2O)]·0.5H2O}n (2) When H2BPDC is replaced by H2SDBA in the self-assembly process, complex 2 is obtained. Complex 2 crystallizes in the orthorhombic crystal system, space group Pcca. Its asymmetric unit consists of half a Cd2+, half a L ligand, half a SDBA2-, half a coordination water molecule and a quarter of a lattice water molecule. As shown in Figure 2a, each Cd2+ ion displays a distorted pentagonal bipyramid geometry surrounded by five equatorial oxygen atom from two SDBA2- ligands (O1, O2, O1#1, O2#1) and a coordinated water molecule, and two axial nitrogen atoms (N1, N1#1) from two L ligands. The Cd-O bond lengths are in the range of 2.317(3)-2.578(3) Å and the Cd-N bond lengths are 2.341(3) Å. The SDBA2- ligands adopting bidentate-chelating modes bridge the Cd2+ to form 4 Environment ACS Paragon Plus

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Figure 2. (a) Coordination environment of Cd2+ ion in complex 2. The hydrogen atoms, coordinated and lattice water molecules are omitted for clarity. Symmetry codes: #1: − x + 2/5, − y, z. (b) View of the two intertwined left-handed and right-handed helices marked by L and R of 2. (c) A single porous 3D network of 2. (d) The 2-fold interpenetrating network of 2.

left- and right-handed helical chains labeled as the L/R running along the crystallographic 21 axis with a long pitch of 26.89 Å (Figure 2b). These left- and right-handed helical chains are further alternately linked by the L ligands to yield a complicated porous 3D network (Figure 2c). From a topological perspective, each Cd2+ ion could be regarded as a 4-connected node. The 3D network can be simplified to a 4-connected net with point symbol {65.8}. In order to minimize the presence of cavities to stabilize the structure in the assembly process, the other identical network is filled in the voids yielding a 2-fold interpenetrating net, as shown in the Figure 2d. The interpenetration can be classified as type Class Ia, Z = 2 (Zt = 2; Zn = 1).24



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3.3. Fluorescent Properties and Detection of Fe3+ MOFs 1 and 2 including d10 ions and auxochromic methylthios both displayed excellent fluorescent property as we expected. Their maximum emission peaks were 472 nm, 458 nm, 466nm, 447 nm, 434 nm, for MOFs 1, 2, 1 aqueous solution, 2 aqueous solution and L, respectively (Figure S3). The luminescence of crystals could be thought to be from intra-ligand emission because the emission peak shapes of MOFs 1, 2 and their aqueous suspensions were similar to the emission peak shape of ligand L. The obvious red-shift compared to the luminescence of ligand L reflected the interaction between the organic linkers and Cd2+. The studies of the selectivity of the sensing ability for various metal cations were performed by gradual addition of nitrate salts of Fe3+, Cu2+, Ce3+, Co2+, Pb2+, Cd2+, Na+, K+, Zn2+, Ni2+ and Cr3+ to the aqueous suspensions of MOFs 1 and 2, with the concentration of 5 × 10−3 M. To our excitement there were significant luminescence attenuation with QP (quench percentage) of 56% for 1 and 53.4% for 2 in the presence of Fe3+ with the concentration of 5.0 × 10-5 M, but the QP of other ions were much lower (less than 23.5% for 1 and 14.7% for 2) at the same concentration as displayed in Figures 3a and 3d. The titration curves showed that the emission intensity of MOFs 1 and 2 both decreased with increasing concentration of Fe3+ from 0.0025 mM to 0.1500 mM (Figures 3b and 3e). Quantitatively, the quenching effects could be treated with the Stern–Volmer equation at low concentrations: Io/I = 1 + Ksv × [M], where Io and I were the luminescence intensities of MOFs 1 and 2 aqueous suspensions before and after the addition of Fe3+ ions, respectively; Ksv was the quenching constant, and [M] was Fe3+ ion concentration. As shown in Figures 3c and 3f, the Ksv were calculated to be 3.63×104 M-1 for 1 and 3.59×104 M-1 for 2. These Ksv values were comparable to those in well-designed solution base organic compounds for sensing of Fe3+ (typical KSV of about 104 M-1).25 3.4. Detection for Cr2O72- and CrO42In order to expand application range of MOFs 1 and 2 as fluorescent probes, the sensing


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(a)

(d)

(b)

(e)

(c)

(f)

Figure 3. The luminescence responses of 1 and 2 dispersed in aqueous solution for Fe3+ ions: (a) Luminescence quenching percentage of 1 in the presence of different metal ions with a concentration of 50 µM. (b) Concentration-dependent luminescence quenching of 1 after adding different



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concentrations of Fe3+ ions. (c) Stern–Volmer plot of I0/I versus Fe3+ concentration in the 1 aqueous suspension (insert: enlarged view of a selected area). (d) Luminescence quenching percentage of 2 in the presence of different metal ions with a concentration of 50 µM (e) Concentration-dependent luminescence quenching of 2 after adding different concentrations of Fe3+ ions. (f) Stern–Volmer plot of I0/I versus Fe3+ concentration in the 2 aqueous suspension (insert: enlarged view of a selected area).

ability for Cr2O72- and CrO42- was investigated by addition of various sodium anion aqueous solutions (i.e., F-, Cl-, Br-, N3-, IO3-, BrO3-, CH3COO-, CO32-, SO42-, CrO42-, Cr2O72-, MoO42-, and WO42-) to the aqueous suspensions of MOFs 1 and 2, with the concentration of the ions being 5×10-3 M. Strikingly, Cr2O72- and CrO42- afforded noteworthy turnoff quenching effect with QP (quenching percentage) of 90.7% , 59.3% for 1 and 84.73%, 57.9% for 2 respectively with the concentration of 2.25×10-4 M but the QP of other ions were much lower (less than 6.17% for 1 and 7.75% for 2) in the same conditions (Figures 4a, 4d ). The titration curves showed that the emission intensity of MOFs 1 and 2 both decreased with increasing concentration of Cr2O72- from 0.0025 mM to 0.3125 mM (Figures 4b and 4e). As shown in Figures 4c and 4f, the Ksv were calculated to be 6.4×103 M-1 for 1 and 4.97×103 M-1 for 2. The detection limits were calculated according to the formula reported in literature.26 Their detection limits for probing Fe3+ were 2.21×10-6 M and 7.14×10-6 M for MOFs 1 and 2, respectively. The detection limits for probing Cr2O72- are 3.76×10-5 M and 4.86×10-5 M for MOFs 1 and 2, respectively. So above results indicated that MOFs 1 and 2 could exhibit high sensitivity for sensing ions. However excellent probes not only needed the high sensitivity but also the anti-interference ability. From the results shown in Figure S4, we could see that the luminescent intensities just had a little attenuation with the mixed ions in the absence of Fe3+ or Cr2O72- , but the luminescent were almost completely quenched when the Fe3+ or Cr2O72- was added into the above solutions. These experiments indicated that MOFs 1 and 2 were highly selective and sensitive for sensing Fe3+ and Cr2O72-.


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(a)

(d)

(b)

(e)

(c)

(f)

Figure 4. The luminescence responses of 1 and 2 dispersed in aqueous solutions for Cr2O72- ions: (a) Luminescence quenching percentage of 1 in the presence of different anions with a concentration of 225 µM (b) Concentration-dependent luminescence quenching of 1 after adding different concentrations of Cr2O72- ions. (c) Stern-Volmer plot of I0/I versus Cr2O72- concentration in the 1



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aqueous suspension (insert: enlarged view of a selected area). (d) Luminescence quenching percentage of 2 in the presence of different metal ions with a concentration of 50 µM (e) Concentration-dependent luminescence quenching of 2 after adding different concentrations of Cr2O72- ions. (f) Stern-Volmer plot of I0/I versus Cr2O72- concentration in the 2 aqueous suspension (insert: enlarged view of a selected area).

In order to use these highly selective and sensitive MOFs for probing ions in environmentally friendly way, the cyclic tests also had been carried out. The results in Figure S5a showed that after three runs, MOFs 1 and 2 could keep their performance and PXRD in Figure S5b showed that their structural were still intact. So MOFs 1 and 2 had the potential to become highly selective, sensitive and environmentally friendly probes for sensing ions.

3.5. Mechanism for Probing Ions To deeply understand the mechanism of luminescent reduction induced by Fe3+, CrO42and Cr2O72- ions, the powder X-ray diffraction patterns (PXRD) as shown in Figure S5b, confirmed that crystalline structures of MOFs 1 and 2 could maintain integrity after titration experiments, so photoluminescence attenuation was not caused by the decomposition of crystalline structures. The emission fluorescence of MOFs 1, 2 and L was detected in aqueous solution. From the results shown in Figure S6a, we could see that MOFs 1 and 2 had obvious fluorescence but L had no fluorescence in the same condition. The Tydall effects of MOFs 1 and 2 showed that MOFs 1 and 2 could effectively disperse in the water and L could not disperse in water (Figure S6b). So above results indicated that the photoluminescence just originated from the MOFs. The luminescence lifetimes of MOFs 1 and 2 before and after addition of ions shown in Figure S7 were the same, the results showed that there were no coordination between ions and MOFs.27 The UV/Vis absorption of the target MOFs and ions were given out in Figure S8. It was obvious that the wide absorption bands from 250 to 425 nm of Fe3+, CrO42- and Cr2O72- ions covered the range of absorption bands of MOFs 1 and 2 and much stronger than other ions in this wavelength range, therefore the UV/Vis absorption of Fe3+, CrO42- and Cr2O72- ions for excitation energy had hindered the absorption of MOFs 1 and 2, thus resulting in a decrease, or even full quenching, of the luminescence


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intensities. This mechanism was consistent with those previously proposed by other group.28-30

4. CONCLUSIONS In summary, two new luminescent Cd(II)-MOFs had been solvothermally synthesized and characterized by infrared spectroscopy, elemental analysis, powder X-ray diffraction and thermogravimetry measurement. Fluorescence titration, anti-interference and cyclic experiments demonstrate that MOFs 1 and 2 are both excellent probes for Fe3+, CrO42and Cr2O72-. The powder X-ray diffraction patterns confirmed that crystalline structures MOFs 1 and 2 could maintain integrity after titration experiments. The UV/Vis absorption of the Fe3+, CrO42- and Cr2O72- ions had hindered the adsorption of MOFs 1 and 2 between 250 to 425nm, so it caused the photoluminescence attenuation of MOFs 1 and 2. This work had confirmed that luminescent MOFs 1 and 2 possessed the potential to serve as practical bifunctional sensor materials.

ASSOCIATED CONTENT Supplementary information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/ Crystallographic data for 1 in CIF format (CIF) Crystallographic data for 2 in CIF format (CIF) AUTHOR INFORMATION Corresponding Author: [email protected] ACKNOWLEDGMENTS We would like to kindly acknowledge the National Natural Science Foundation of China (No. 21371092), and National Basic Research Program of China (2010CB923303). REFERENCES

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For Table of Contents Use Only Two New Luminescent Cd(II)-MOFs as Bi-functional Chemosensors for Detection of Cations Fe3+, Anions CrO42- and Cr2O72- in Aqueous Solution Shuguang Chen, Zhenzhen Shi, Ling Qin, Hailang Jia, Hegen Zheng*

Two new luminescent Cd(II)-MOFs have been solvothermally synthesized and characterized by infrared spectroscopy, elemental analysis and powder X-ray diffraction. Fluorescence titration experiments, cyclic and anti-interference demonstrate that Cd(II)-MOFs are both excellent probes for Fe3+, CrO42- and Cr2O72-. The mechanisms of quenching are also deeply studied.


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Two New Luminescent Cd(II)-MetalâOrganic Frameworks as

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