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Antiferromagnetic Copper(II) Metal−Organic Framework Based Quartz Crystal Microbalance Sensor for Humidity Zhuoqiang Zhou,† Ming-Xing Li,*,‡ Luyu Wang,‡ Xiang He,‡ Tao Chi,*,§ and Zhao-Xi Wang*,‡ †

Department of Pharmaceutical Engineering, College of Materials & Energy, South China of Agricultural University, Guangzhou 510642, People’s Republic of China ‡ Department of Chemistry, Center for Supramolecular Chemistry and Catalysis, Shanghai University, Shanghai 200444, People’s Republic of China § College of Information Technology, Shanghai Ocean University, Shanghai 201306, People’s Republic of China S Supporting Information *

ABSTRACT: A novel copper metal−organic framework (MOF) [Cu3L2(H2O)2.75]·0.75H2O·1.75DMA (H3L = 4-(2-carboxyphenoxy)-isophthalic acid, DMA = dimethylacetamide) has been synthesized and structurally characterized by elemental analyses, IR spectroscopy, and singlecrystal X-ray diffraction. Compound 1 shows a three-dimensional architecture with a sqc topology net where the [Cu2(COO)4] unit was viewed as a node. Magnetic studies indicate that strong antiferromagnetic coupling with J = −159.0(9) cm−1 dominates in the compound. As a sensor, the compound based on quartz crystal microbalance (QCM) exhibits good linearity humidity sensing properties after being exposed to various relative humidity environments at room temperature. The resulting sensitivity is about 28.7 Hz/%RH with a good linearity coefficient of 0.993.

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INTRODUCTION Over the past two decades, metal−organic framework (MOF) materials have attracted much research interests in the field of coordination chemistry, owing to their intriguing structural topologies and wide potential applications such as gas storage and separation, heterogeneous catalysis, enantioselective separation, nonlinear optics, ferroelectrics, magnetism, and smallmolecular sensing.1−10 Among their useful properties, sensing is still largely unexplored to date.11−13 Only several MOF sensors aimed at the convenient detection of explosives, chemical vapors, and O2 gas have been developed.14−16 In particular, humidity sensing is of great importance in the field of environment, agriculture, medicine, and industrial facilities.17−19 Up to the present, several kinds of materials such as ceramics, polymers, and nanometer materials have been used for monitoring humidity.20−22 Compared with those materials, MOFs are considered ideal candidates for humidity sensing material due to their large pore diameters, high porosities, and featuring opportunities for further functionality.23−26 However, there are only several MOFs investigated for this purpose, such as Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate) thin film,27 Ln3+ MOF luminescent humidity sensors,28 Ti-based MOF (MIL-125) humidity sensor with amine functionalization ligand,29 and Cu(I) MOF naked-eye colorimetric humidity sensor.30 Quartz crystal microbalance (QCM), as a typically masssensitive device, can determine a small mass change down to a nanogram level.31 Due to the advantages of high stability and © 2017 American Chemical Society

good sensitivity, the QCM is widely used under vacuum, in gas phase, and, more recently, in liquid environments. Since King first introduced QCM into analytical chemistry in 1964,32 there are many sensing materials, such as modified nitrated polystyrene, Nafion-Ag, polypyrrole, and so on, coated on the electrode of QCM to detect different vapors.33−35 Although many fruitful works have been documented in nanostructured material-based QCM sensors, MOF-based QCM sensors for different vapors have been rarely investigated.36−39 For instance, Meilikhov employed a binary Janus copper(II) porous coordination polymer coating on QCM sensor for methanol sensing.40 Meanwhile, to the best of our knowledge, no cases of MOF humidity sensor combined with QCM have been reported. As we know, polycarboxylates are widely employed to construct MOFs with desired structures and functional properties.41−45 Several well-known MOFs were prepared by rigid polycarboxylates such as terephthalate (MOF-5) and 1,3,5-benzenetricarboxylate (HKUST-1, MIL-100).46−48 While, as an asymmetric semirigid V-shaped tricarboxylate ligand,49−52 4-(2-carboxyphenoxy)-isophthalic acid (H3L) has been not fully capitalized to build MOFs,53,54 it is noted that one of its MOFs, [Zn3L2(4,4′-bpy)2·H2O] (4,4′-bpy = 4,4′-bipyridine), exhibits a unique luminescent response to methanol.55 With this Received: September 17, 2017 Revised: October 5, 2017 Published: October 16, 2017 6719

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background in mind, we utilized H3L as a ligand successfully and prepared a three-dimensional (3-D) porous Cu(II) MOF [Cu3L2(H2O)2.75]·0.75H2O·1.75DMA (1), with a sqc topology, which exhibits good humidity sensing properties coated on quartz crystal microbalance (QCM). Herein, we report the structure, magnetic properties, and humidity sensing of 1 in detail.

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Table 1. Crystallographic Data and Structure Refinement for 1

EXPERIMENTAL SECTION

Materials and Methods. All reagents and solvents employed in the present work were of analytical grade as obtained from commercial sources without further purification. The ligand (H3L) was purchased from Jinan Henghua Company. Elemental analyses for C, H, and N were performed on a Vario EL-III elemental analyzer. The FT-IR spectrum was recorded using KBr pellet in the range from 4000 to 400 cm−1 on a Nicolet Avatar A370 spectrophotometer. Powder X-ray diffraction (PXRD) data were collected on a Rigaku D/Max-2200 diffractometer with Cu Kα radiation (λ = 1.5406 Å) over the 2θ range of 5−50° to check the phase purity of bulk materials. Thermogravimetric analysis (TGA) was performed on a Netzsch STA 449C thermal analyzer at a heating rate of 10 °C min−1 in air. Magnetic susceptibilities were carried out on a Quantum Design MPMS-XL7 SQUID magnetometer in a field of 1 kOe. Diamagnetic corrections were made with Pascal’s constants. For the sensing measurements, sample crystals were used directly without further activation and grind. Sensing properties were measured on quartz crystal microbalance (QCM) according to the modified literature method reported previously.56−58 Synthesis of [Cu3L2(H2O)2.75]·0.75H2O·1.75DMA (1). A mixture of CuCl2·2H2O (34.0 mg, 0.2 mmol) and H3L (30.6 mg, 0.1 mmol) in 6 mL of oH2O and 2 mL of dimethylacetamide (DMA) was sealed in a 25 mL Teflon-lined stainless steel autoclave and heated at 85 °C for 3 days. After cooling to room temperature at a rate of 5 °C/h, blue block crystals were obtained in 75% yield based on H3L. Elemental analysis calcd (%) for C37H36.75O19.25N1.75Cu3 (1004.6): C, 44.24; H, 3.69; N, 2.44. Found: C, 44.15; H, 3.38; N, 2.33. IR (KBr cm−1): 3448(s), 3077(w), 2937(w), 1619(s), 1597(s), 1478(w), 1443(m), 1396(s), 1255(w), 1227(s), 1163(w), 1096(m), 765(s), 690(m), 653(m), 531(m). X-ray Crystallography. Single-crystal X-ray diffraction data for compound 1 was collected on a Bruker SMART APEX-II CCD diffractometer using graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å) using the φ−ω scan technique. Data reduction was conducted with the Bruker SAINT package. Absorption correction was performed using the SADABS program. The structure was solved by the direct methods and refined on F2 by full-matrix least-squares using SHELXL program59 with anisotropic displacement parameters for all non-hydrogen atoms. H atoms were introduced in calculations using the riding model. The solvent of water and DMA molecules in the crystal are highly disordered, and the SQUEEZE subroutine of the PLATON software suit was conducted.60 Crystallographic data are listed in Table 1. CCDC 1481536 contains the details.

compound

1

formula formula weight crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z Dc (g cm−3) μ (mm−1) F (000) Rint GOF R1, wR2 [I > 2σ(I)] R1, wR2 (all data)

Cu3C30H19.5O16.75 838.58 tetragonal I4/m 20.929 (1) 20.929 (1) 18.232(2) 90 90 90 7986.0(1) 8 1.395 1.647 3364 0.0432 1.106 0.0776, 0.2346 0.0909, 0.2448

lengths of Cu−O range from 1.946(5) to 1.986(6) Å in basal plane, while the apical Cu−O bonds are a little longer (1.985(9)−2.4584(14) Å). The shortest Cu···Cu distances are 2.627(2) and 2.634(2) Å. Meanwhile, the full deprotonated L3− ligand displays (η1:η1)-(η1:η1)-(η1:η1)-μ6 coordination mode to link six adjacent Cu ions with three bidentate bridging carboxylate groups. The similar coordination mode was observed in its one cobalt compound.53 In compound 1, two neighboring copper ions are bridged by four carboxyl groups to form a paddle-wheel [Cu2(COO)4] secondary building unit (SBU) (Figure 1b). Each SBU connects four organic ligands, and each ligand binds three SBUs to generate a 3-D metal−organic framework. The open-framework structure of 1 contains two distinct pores with coordinated water molecules toward the inside (Figure 1c). The big pore presents windows with size about 1.6 × 4.8 Å2 leading to form a narrow channel. In addition, some disorder solvent water and DMA molecules occupy the pores. After removing all of the guest molecules from the pores, the total accessible volume is 30.2% per unit cell volume calculated by PLATON. To better understand the 3-D structure, topologic analysis is performed with TOPOS program package.61 By regarding each Cu2−SBU as a four-connected node and each L3− as a three-connected node, the overall 3-D framework can be rationalized as a binodal 3,4-coordinated net exhibiting sqc topology with the point symbol (4·82)4(42·82·102)2(86)62−64 (Figure 1d). Magnetic Properties. Temperature-dependence molar susceptibility measurements of the crystalline sample of 1 were carried out on a Quantum Design MPMS-XL7 SQUID magnetometer in an applied magnetic field of 1 kOe over the temperature range 2−300 K. Plot of χMT versus T for compound 1 is depicted in Figure 2. At room temperature, the χMT value of 1 is 0.52 emu K mol−1, much lower than the spin-only value of 0.75 emu K mol−1 based on two uncoupling copper(II) ions (S = 1/2 and assuming g = 2.0). When the temperature is lowered, the χMT value decreases rapidly to 0.03 emu K mol−1 at 70 K, suggesting the presence of a strong antiferromagnetic exchange interaction in 1. According to the crystal structure, 1 consists of Cu2 dimers where two Cu2+ ions are linked by four carboxyl groups to form a paddle-wheel unit, which is similar to the structure of

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RESULTS AND DISCUSSION Structure of [Cu3L2(H2O)2.75]·0.75H2O·1.75DMA (1). Compound 1 crystallizes in the tetragonal I4/m space group and contains a complicated 3-D framework. After squeezing the solvent, the asymmetric unit possesses four distinct Cu(II) ions (the occupancies of Cu1/Cu4 and Cu2/Cu3 are 0.5 and 0.25, respectively), one fully deprotonated L3− anion, four coordinated water molecules (the occupancies of O8/O9, O10, and O11 are 0.5, 0.125, and 0.25, respectively) (Figure 1a). The four Cu(II) metal centers have distorted square pyramidal geometry with different coordination environments. For the square pyramidal geometry of the Cu(II) ions, the basal plane consists of four carboxyl oxygen atoms from four carboxylates, while the apical site is occupied by a water molecule. The bond 6720

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Figure 2. Temperature dependence of magnetic susceptibilities of 1 in an applied field of 1 kOe. Solid line represents the best fit of the data.

show a strong overlap with the magnetic orbitals dx2−y2 on both copper(II) ions.65 Taking into account that this coupling is the most important one, we can neglect the coupling between different Cu2 dimers. Based on the isotropic Hamiltonian H = −2JS1S2, the experimental data in the whole temperature range were fitted to the Bleaney−Bowers equation modified by Kahn and co-workers to take into account some paramagnetic impurity for an isotropically coupled pair of S = 1/2 ions.66−68 χM = (1 − ρ)

2Ng 2β 2 Ng 2β 2 1 × + ρ −2J / kT kT 2kT 3+e

where χM is the molar magnetic susceptibility of the Cu2 dimer, ρ is the percentage of paramagnetic impurity, and other symbols have their usual meanings. The best-fit parameters reproducing satisfactorily magnetic properties of 1 as shown in Figure 2, are g = 2.288(8), J = −159.0(9) cm−1, and ρ = 0.0293(7), with an agreement factor of R = ∑[(χMT)calc − (χMT)obs]2/∑(χMT)obs2 = 1.0 × 10−5. The fitting results correspond to other paddlewheel copper compounds.69 Humidity Sensing Properties. The sensing behaviors of 1 have been investigated by QCM transducer at room temperature. First, we studied the selectivity of the QCM sensor. Response of the QCM sensor upon exposure to different vapors containing ethylbenzene, n-hexane, formaldehyde, benzene, ethanol, acetone, xylene, and water, is presented in Figure 3a. When exposed to selected saturated vapors, the 1-based QCM sensor shows a frequency change of 620, 918, 753, 1002, 569, 339, 132, and 4162 Hz to ethylbenzene, n-hexane, formaldehyde, benzene, ethanol, acetone, xylene, and water, respectively. Compared to the response of the other vapors, the 1-based QCM sensor exhibits a significant frequency change to water. These results indicated that the QCM sensor shows a good selectivity toward water vapor, which is due to the oxygen-rich pore surface characteristics and size effect.38 As described in the structure, there are many oxygen atoms from coordinated water molecules and L3− ligand exposed on the pore surface, which leads to the hydrophilic channels in 1. Therefore, water molecules can easily enter the channels and adsorb on active sites (coordinated water). To further explore humidity sensing properties of the QCM sensor, we evaluate its response and stability. Figure 3b shows the relationship between the frequency change shifts and humidity ascending process in the RH of 17.2, 33.1, 43.2, 75.0,

Figure 1. (a) Asymmetric unit of 1 with ellipsoids drawn at 50% probability level; (b) coordination mode of L3−; (c) 3-D MOF; and (d) sqc topologic net. H atoms and solvent are omitted for clarity.

Cu(CH3COO)2. In general, the carboxylate-bridged compounds normally present stronger antiferromagnetic coupling since they 6721

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Figure 4. Short-term repeatable and reversible sensing response to 97.6% relative humidity with 1-based QCM sensor.

Figure 5. Response time and recovery time of 1-based QCM sensor.

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CONCLUSIONS In this work, a novel Cu(II) coordination polymer [Cu3L2(H2O)2.75]·0.75H2O·1.75DMA based on a semirigid V-shaped tricarboxylate ligand has been successfully synthesized under hydrothermal conditions. The magnetism and humidity sensing properties of 1-based QCM sensor have been investigated. Compound 1 shows a 3-D framework with a sqc topology net where the [Cu2(COO)4] unit was viewed as a node. Magnetic studies indicated that compound 1 presents strong antiferromagnetic interactions with J = −159.0(9) cm−1 between the Cu ions. The 1-based QCM sensor exhibits good selectivity to water vapor and stable humidity sensing properties.

Figure 3. (a) Frequency response of the 1-based QCM sensor to a variety of solvent vapors under air conditions (298 K, 56% RH). (b) Frequency response to relative humidity. (c) Linear behavior.

and 97.6% for the sensor under room temperature (the air RH is 56.0%). It can be seen from Figure 3b that the resonant frequency change shift increased with increasing relative humidity. Derived from Figure 3b, Figure 3c was given to evince highly linear behavior of the sensor. The resulting sensitivity, calculated as ΔHz/ΔRH, is about 28.7 Hz/%RH with a good linearity coefficient of 0.993. After a steady frequency had been obtained in normal atmosphere, the humidity of 97.6% RH is introduced to check the stability of the coated sensor. Plot of time-dependent frequency response for the sensor is presented in Figure 4. Obviously, it is seen that the frequency shift was still high within 500 s. Thus, the QCM sensor coated with compound 1 is very stable in humidity circumstances, which may be caused by the open windows of the pore and strong hydrogen bond interaction between coordination water and vapor molecules. Besides, as is shown in Figure 5, the response time and recovery time of 1-based QCM sensor toward 97.6% RH is approximately 30 and 18 s, respectively, indicating its good sensing performance.70

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.7b01318. Selected bond lengths, IR, PXRD, and TGA for 1 (PDF) Accession Codes

CCDC 1481536 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_ [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. 6722

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: +86-21-66132670. ORCID

Ming-Xing Li: 0000-0003-0000-9876 Zhao-Xi Wang: 0000-0002-2689-7034 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Z.-X.W. acknowledges the Natural Science Foundation of Shanghai (16ZR1411400), and T.C. acknowledges the National Natural Science Foundation of China (61561027). We thank Dr. Min Shao (Laboratory for Microstructures, SHU) for single-crystal X-ray diffraction data collection and gratefully acknowledge helpful discussions with Prof. Jiaqiang Xu (SHU).

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