Conventional and Mechanochemical Syntheses of Copper(I) Iodide

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Conventional and Mechanochemical Syntheses of Copper(I) Iodide Luminescent MOF with Bis(amidoquinoline) and Its Application for the Detection of Amino Acid in Aqueous Solution Eunji Lee,† Huiyeong Ju,† Jong Hwa Jung,† Mari Ikeda,‡ Yoichi Habata,*,§ and Shim Sung Lee*,† †

Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, South Korea Education Center, Faculty of Engineering, Chiba Institute of Technology, 2-1-1 Shibazono, Narashino, Chiba 275-0023, Japan § Department of Chemistry, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan Downloaded via UNIV OF MISSOURI COLUMBIA on January 1, 2019 at 08:07:24 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

‡

S Supporting Information *

ABSTRACT: Formation of a copper(I) iodide cluster based luminescent metal−organic frameworks (LMOFs) and its utilization for the detection of cysteine (Cys) in aqueous solution are reported. The reaction of bis(amidoquinoline) ligand (L) with copper(I) iodide afforded an LMOF {[(Cu2I2) L2]·2DMSO}n (1) with a 44-sql topology linked by Cu2I2 clusters as a thermodynamic product. Time- and temperaturedependent PXRD experiments confirmed that the entire formation process for 1 is kinetically and thermodynamically controlled. Interestingly, LMOF 1 was also obtained under the mechanochemical condition. Moreover, LMOF 1 dispersed in water shows a selective quenching for Cys over other amino acids due to the strong affinity of Cys to copper(I) iodide. On the basis of the NMR data of L isolated from the decomposition of 1, the decomposition−displacement mechanism was proposed for the sensing of Cys. This result might be utilized for the practical detection of Cys because the sensing material can be prepared simply, and the sensing process is performed in aqueous media.

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carboxamidoquinline,28 hemicyanine dye,29 and iminocoumarin30 have been reported. Despite of a wide range of fluorescent sensors for amino acids, the large portion is carried out in water/ organic mixed media,31,32 which limit their application in biological system. Therefore, the development of LMOFs for the detection of Cys in aqueous solution is a challenging task. Among the LMOFs, polynuclear copper(I) iodide cluster based coordination networks are particularly attractive because of their strong photoluminescence (PL) assigned to MLCT with some mixing of XLCT characters.33−37 The solvatochromic behaviors of the porous [CunIn]-based LMOFs via guest exchange and their use in detecting small organic molecules including VOCs have been introduced.35,38 In spite of the huge progress on the [CunIn] based LMOFs, the application in amino acid sensing is still an unexplored area. The reason is probably that amino acids are nonvolatile and that the access via guest exchange is difficult in aqueous solution. Considering the sulfur content in Cys and the thiaphilicity of copper(I),39 the expected stronger bonding of S−Cu+ over that of N−Cu+ might serve an opportunity to rationalize a Cys sensing system as depicted in Scheme 1. In connection with this reason, we have proposed a formation of [CunIn] cluster based

INTRODUCTION Metal−organic frameworks (MOFs) and coordination polymers (CPs) often exhibit interesting physical properties including gas storage, magnetism, and luminescence.1−9 In particular, the luminescent MOFs (LMOFs) provide opportunities to extend their applications as organic light-emitting diodes, molecular switches, and chemosensors.6−17 In the past decade, LMOFs were employed for sensing small organic molecules including volatile organic compounds (VOCs), explosive nitroaromatic species, and amino acids.10−19 Beyond their role as residues in proteins, amino acids are crucially involved in various processes such as neurotransmitter transport and biosynthesis.20 Thus, detection of amino acids is essential in the nutritional analysis21 and the diagnosis of diseases such as Alzheimers22 and pancreatitis.23 In particular, the sensing of cysteine (Cys) in biological fluids has been a surge of interest because it is one of the semiessential protein-building amino acids and a precursor in the pharmaceutical and personalcare industries. Among the generally employed analytical techniques,24−27 which include HPLC, luminescent/colorimetric detection,24,25 capillary electrophoresis,26 and electrochemical methods,27 the fluorescence probe for Cys detection is remarkable because of its rapid sensing with high sensitivity. Some fluorescent probe for detection of Cys, utilizing copper(II) complex of bi-8© XXXX American Chemical Society

Received: September 7, 2018

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DOI: 10.1021/acs.inorgchem.8b02549 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Scheme 1. Cys Sensing (Turn-Off) Using Copper(I) Iodide Cluster based LMOF via Replacement Mechanism

LMOF which might be decomposed to the weak or nonemissive free ligand via replacement mechanistic process. On the basis of the above suggestion, we have employed bis(amidoquinoline) ligand (L, Scheme 2), which might act as a Scheme 2. Preparation of Copper(I) Iodide Complexes 1 and 2

semiflexible linker via N−Cu+ bonding to afford an LMOF. In fact, L has been reported by Cain group in 1967 together with a series of bis quaternary ammonium heterocycles, as potential antitumor agents.40 Here, we report the preparation of an emissive 2D copper(I) iodide coordination network with L which offers an opportunity to explore the detection of Cys via the naked eye in aqueous solution. To the best of our knowledge, such amino acids sensing system in water utilizing copper(I) iodide cluster based LMOF has not yet been documented.

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RESULTS AND DISCUSSION Preparation of Copper(I) Iodide Complex (1). Ligand L was prepared as described previously40 and confirmed by 1H and 13 C NMR since its NMR data have not yet been reported (Figure S1). It is notable that the reaction of L with CuI in dichloromethane/acetonitrile yielded two products (1 and 2) with different photophysical properties depending in reaction time (Scheme 2). For example, a greenish yellow precipitate (termed 2) appeared after stirring of the reaction mixture for 1 h, and continuous stirring for another 24 h under the same condition afforded an orange emissive solid (termed 1). The recrystallization of 1 yielded X-ray quality crystals. Powder X-ray diffraction (PXRD) analysis has been performed to monitor the time- and temperature-dependent kinetic and thermodynamic products. PXRD and PL Studies. To monitor the influence of reaction time on the copper(I) iodide complex formations of L systemically, time-dependent PXRD experiments were performed by varying the reaction time from 1 to 24 h with stirring at room temperature (Figure 1a). When the reaction times are in the range of 1−5 h, the PXRD patterns of the products (denoted with greenish-yellow color) were not changed, indicating that 2 is the only product in this range. After 7 h, some new peaks (denoted with orange reciprocal triangles) appear which correspond to 1, indicating the formation of a mixture of 2

Figure 1. (a) PXRD patterns and (b) PL spectra for the solid products isolated from the reaction mixture by varying the reaction times (1−24 h) at room temperature, showing the PL changes from greenish-yellow (2) to orange (1) colors.

and 1. After 12−24 h, the evidence of 2 disappears, and only 1 exists. At 50 °C, the same reaction afforded the orange solid of 1 (Figure S2). The solid-state PL spectra for the products isolated with different reaction times were obtained at room temperature (Figure 1b). Product 1 exhibits a greenish yellow emission at 560 nm, and the longer reaction times show a gradual redshift of the maxima emission. Eventually, the reaction time of 24 h exhibits an orange emission at 590 nm indicating the existence of product 2 which is likely due to a cluster-centered excited state B

DOI: 10.1021/acs.inorgchem.8b02549 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 2. Crystal structure of 1, {[(Cu2I2)L2]·2DMSO}n: (a) core coordination unit, (b) view of the 44-sql net of the 2D coordination polymer, (c) packing with A−B−A−B stacked pattern, and (d) closer view of A and B layers. Non-coordinating solvent molecules are omitted.

with mixed halide-to-metal charge transfer.41−49 From the combined results of the PXRD, PL, and high-temperature (50 °C) reaction, it is concluded that the conversion of 2 to 1 is in accord with complex 2 being a kinetic product, with complex 1 being a thermodynamic product. Crystal Structure of 1. The recrystallization of 1 from DMSO/diethyl ether yielded single crystals. X-ray analysis reveals that 1 is a square-grid type 2D coordination polymer of the formula {[(Cu2I2)L2]·2DMSO}n (Figure 2). The asymmetric unit contains a half of Cu2I2 cluster and one L ligand. Each tetrahedral Cu atom in the Cu2I2 cluster is bound to two iodide atoms and two nitrogen atoms from different L ligands in a twisted conformation. Accordingly, the Cu2I2 cluster links four L ligands via Cu−N bond [2.108(3) Å], forming a 2D undulated net, taking Cu2I2 clusters as 4-connected nodes and the 2D layer has a 44-sql topology that extends to the ab-plane (Figure 2b). Notably, the 2D sheet structure of 1 is highly undulated with a thickness of 14 Å. Thus, the layers in 1 are stacked together in an A−B−A−B fashion forming a pseudo-3D structure (Figure 2c,d). PL spectra of L and 1 (Figure 3) and their quantum yields in the solid state were measured at room temperature. Ligand L is emissive in the blue region with the peak centered at λmax = 424

Figure 3. PL spectra of L and 1 in the solid state at room temperature (excitation at 365 nm).

nm. As mentioned, 1 exhibits an orange emission at 590 nm. The absolute quantum yields for L and 1 at 365 nm were determined to be Φ = 0.034 and 0.095, respectively. C

DOI: 10.1021/acs.inorgchem.8b02549 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry In the TGA of complex 1, the weight loss of 11.43% was observed over 200 °C, corresponding to the removal of two DMSO molecules in the lattice (calcd 11.37%) (Figure S3). Then, the curve shows a plateau until 350 °C, indicating the framework being stable at this temperature. At the higher temperature, however, the network structure begins to decompose. Mechanochemical Preparation of 1. On grinding the solid mixture of CuI and L in our preliminary work, a significant PL change was observed under the excitation by a UV lamp (Figure 4a). On the basis of this observation, we assumed that

Figure 4. (a) Mechanochemical reaction process. (b) Confirmation of product 1 via the PXRD patterns.

Figure 5. (a) PL spectral changes of 1 (1 mg dispersed in 1 mL H2O) in the presence of amino acids (3 mM). Inset: photograph of 1 after the addition of amino acids in water under the UV lamp (365 nm). (b) PL quenching efficiencies (I0/IQ − 1) obtained from different amino acids by 1 (I0 and IQ: the emission intensities before and after addition of amino acids, respectively).

the solvent-assisted mechanochemical reaction between CuI and L may occur,50,51 so the mechanochemical preparation of the CuI−L system by manual grinding (30 min) was accomplished in the presence of several drops of solvents. Interestingly, complex 1 was also obtained under the mechanochemical condition in the presence of 3 drops of CH3CN and 1 drop of DMSO for 30 min, as confirmed by comparative PXRD patterns (Figure 4b) and the PL spectra (Figure S4). PL Sensing for Cysteine (Cys). In order to detect the organic guest molecules such as pharmaceuticals, carcinogens, nitro-containing explosives, and amino acids, several types of LMOFs have been utilized.17,18,28−32 The observed luminescent nature of 1 encouraged us to investigate the possible detection of guest molecules. For this reason, the solid particles of 1 prepared via the conventional process (Scheme 2) were dispersed in water (average particle size: 1941 nm in 1 mg/1 mL H2O, Figure S5). Upon excitation of this dispersed aqueous solution at 365 nm, an orange emission (590 nm) was observed (Figure 5a). To monitor the PL changes induced by amino acids, the different amino acid solutions prepared (3 mM) were added to the

dispersed solution of 1 (1 mg/1 mL H2O). Interestingly, Cys showed the highest PL quenching efficiency among 12 different amino acids used (Figure 5). While no significant changes were observed by addition of other amino acids. Time-dependent PL spectra of 1 with Cys (3 mM) were collected in water. In this case, the emission intensity at 590 nm decreased gradually and minimized after 8 min, indicating the equilibrium state at this point (Figure S6). Notably, an isosbestic point was observed at 509 nm as the reaction proceeded. Thus, all the PL measurements in the control experiments were performed after 8 min upon addition of each amino acid. Given the high selective recognition of Cys, the use of 1 was tested as a “Turn-Off” sensor in aqueous media. Upon addition of Cys into a solution of 1, the emission intensity at 590 nm decreases linearly in the range of 0−1200 μM of Cys (inset in Figure 6), indicating that 1 is suitable for the detection of Cys quantitatively in the moderate condition. D

DOI: 10.1021/acs.inorgchem.8b02549 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

disperse solution of 1, the orange emissive color changed to nonemissive, forming a colorless precipitate. After washing with dilute aqueous NaOH and drying, the 1H NMR spectrum of the precipitate in DMSO-d6 was obtained (Figure 7d). By comparing with the NMR spectra of L (Figure 7b) and 1 (Figure 7c), the precipitate (Figure 7d) was confirmed as a free form of L which was recovered from the decomposition of 1. This result suggests that the CuI−Cys complex species could be more stable than that of the 2D coordination polymer 1 in the presence of Cys. Indeed, Rigo et al.39 reported NMR titration data for a 1:1 complexation of Cu+−Cys in aqueous solution (K1:1 = 7.9 × 109 M−1) which stabilizes by the strong binding of the thiol group to copper(I). In other words, Cys acts as an efficient ligand for Cu(I), leading to the decomposition of the 2D network to release L. We also confirmed that the emissive 1 was regenerated when CuI was added to the isolated L solution. On the basis of these observations, we propose a decomposition−displacement mechanism54,55 for sensing (Figure 7a).

Figure 6. PL spectra of 1 (1 mg dispersed in 1 mL of H2O) after 8 min upon addition of Cys (0−1200 μM) in water (λex = 365 nm). Inset: the emission intensities at 590 nm as a function of [Cys].

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Using a Stern−Volmer equation (I0/IQ = 1 + KSV [Cys]) for the data in Figure 6, the quenching constant (KSV) was obtained. The Stern−Volmer plot is almost linear at low concentrations (0−350 μM, Figure S7), suggesting the static quenching process is predominant in this region. On the basis of the linear part, KSV is calculated to be 6.128 × 102 M−1 (R = 0.9914). The plot is deviated from linearity and curves upward at high concentration range. The luminescence decay experiments revealed that the average excited-state life times of 1 and 1 + Cys are 1.1 and 0.6 μs, respectively (Figure S8). It is known that the lifetime is reduced in the presence of the quencher when the dynamic quenching process is predominant. Overall, the observed quenching result could be preceded through both static and dynamic processes.52,53 Control experiments were performed using alanine (Figure S9). In order to understand the possible quenching mechanism, an aqueous solution of 1 in the presence of Cys was monitored. As shown in Figure 7, 5 equiv of Cys was added to the aqueous

CONCLUSION In summary, a copper(I) iodide cluster based 2D LMOF 1 with a 44-sql topology was prepared from the assembly reaction with bis(amidoquinoline) ligand (L). LMOF 1 was also prepared quantitatively under the mechanochemical condition. LMOF 1 shows a selective PL quenching for Cys compared to other amino acids in aqueous solution. The observed sensing ability for Cys appears to be unprecedented and its decomposition− displacement sensing mechanism is proposed. Despite some limitations of the LMOF-based sensing system for the practical use, the observed results could be a meaningful progress for the amino acid detection because of its reasonable performances including the simple procedure and reproducible result in aqueous solution.

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EXPERIMENTAL SECTION

General. Chemicals and solvents employed in the synthetic works were reagent-grade and used as received. NMR spectra were obtained by using a Bruker DRX 300 spectrometer. FT-IR spectra were recorded on a ThermoFisher Scientific Nicolet iS 10 FT-IR spectrometer. Thermogravimetric analyses were recorded on a TA Instruments TGAQ50 thermogravimetric analyzer. ESI-mass spectra were obtained on a Thermo Scientific LCQ Fleet spectrometer. The PL spectra were performed on a RF-5301 spectrophotometer. The absolute quantum yields were measured with a Hamamatsu Quantaurus-QY C11347−11 absolute PL quantum yields measurement system. The PXRD experiments were performed in a transmission mode with a Bruker GADDS diffractometer. The elemental analysis data was obtained by a Thermo-Fisher Scientific Flash 2000 elemental analyzer. Preparation of L. Ligand L was prepared via the modified procedure of the reported method in the literature.40 To a stirred solution of terephthaloyl chloride (1.00 g, 4.93 mmol) in 50 mL of dichloromethane in a round-bottomed flask, were added 5-aminoquinoline (1.47 g, 10.2 mmol) and triethylamine (2.10 g, 20.7 mmol). The reaction mixture was stirred for 4 h, and the resulting pale-yellow precipitate was collected by filtration, washed with water, methanol, acetone, and diethyl ether. The solid product was dried in a vacuum oven. Yield: 75%. 1H NMR (300 MHz, DMSO-d6): δ 10.78 (s, 2 H, NH), 8.97−7.57 (m, 16 H, Ar). 13C NMR (75 MHz, DMSO-d6): 166.40, 151.09, 148.67, 135.05, 134.50, 132.63, 131.57, 129.52, 129.27, 128.02, 127.77, 124.66, 124.23, 121.62. IR (KBr pellet): 3247, 3156, 3064, 3035, 3011, 1641, 1596, 1542, 1497, 1480, 1408, 1364, 1330, 1300, 1277, 1250, 1075, 914, 824, 789, 695, 670, 658, 644 cm−1. Mass spectrum: m/z = 419.25 [C26H19N4O2]+. Preparation of {[(Cu2I2)(L)2]·2DMSO}n (1). CuI (10.2 mg, 0.053 mmol) in acetonitrile (1 mL) was added to a solution of L (20.1 mg, 0.048 mmol) in dimethyl sulfoxide (DMSO, 1 mL). A greenish-yellow

Figure 7. (a) Representation of decomposition-displacement sensing mechanism. 1H NMR spectra of (b) L, (c) complex 1, and (d) precipitate isolated from a mixture of 1 and Cys in DMSO-d6. E

DOI: 10.1021/acs.inorgchem.8b02549 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry precipitate was obtained after stirring for 1 h. The precipitate was filtered off, washed with diethyl ether, and dried in air (yield 80%). The precipitate was dissolved in DMSO and vapor diffusion of diethyl ether into the DMSO solution yielded X-ray quality crystals. Mp: over 250 °C (decomp). IR (KBr pellet): ν = 3228, 3057, 2982, 2902, 1667, 1650, 1589, 1540, 1502, 1474, 1411, 1366, 1325, 1302, 1279, 1252, 1209, 1179, 1074, 1040, 955, 805, 703, 661, 644 cm−1. Anal. Calcd for [C28H24CuIN4O3S]: C 48.95, H 3.52, N 8.15, S 4.67. Found: C 49.06, H 3.58, N 8.23, S 4.49.

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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.inorgchem.8b02549. NMR spectra of L, PXRD patterns, TGA data for 1, PL spectra, particle size distribution, Stern−Volmer plots (PDF) Accession Codes

CCDC 1864198 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.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (Y.H.). *E-mail: [email protected] (S.S.L.). ORCID

Eunji Lee: 0000-0002-3031-943X Jong Hwa Jung: 0000-0002-8936-2272 Shim Sung Lee: 0000-0002-4638-5466 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by NRF (2016R1A2A205918799 and 2017R1A4A1014595), South Korea. The Support Program for Strategic Research Foundation at Private Universities (S1201034) and KAKENHI-PROJECT-17K05844 from the Ministry of Education, Sports, Science and Technology of Japan are acknowledged.

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REFERENCES

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DOI: 10.1021/acs.inorgchem.8b02549 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.8b02549 Inorg. Chem. XXXX, XXX, XXX−XXX