A novel tetranuclear copper(I) iodide metal-organic cluster [Cu4I4

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A novel tetranuclear copper(I) iodide metal-organic cluster [Cu4I4(Ligand)5] with highly selective luminescence detection of antibiotic Guang-Ning Liu, Ruo-Yu Zhao, Rang-Dong Xu, Xu Zhang, Xue-Na Tang, Qing-Juan Dan, Yun-Wei Wei, Yan-Yan Tu, Qi-Bing Bo, and Cuncheng Li Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00819 • Publication Date (Web): 20 Jul 2018 Downloaded from http://pubs.acs.org on July 23, 2018

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Crystal Growth & Design

A novel tetranuclear copper(I) iodide metal-organic cluster [Cu4I4(Ligand)5] with highly selective luminescence detection of antibiotic Guang-Ning Liu,*,a,b Ruo-Yu Zhao,a Rang-Dong Xu,a Xu Zhang,a Xue-Na Tang,a Qing-Juan Dan,a Yun-Wei Wei,a Yan-Yan Tu,a Qi-Bing Bo,a and Cuncheng Li*,a a

School of Chemistry and Chemical Engineering, University of Jinan, Jinan Shandong

250022, PR China b

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure

of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China E-mail: [email protected] (G.-N. Liu), [email protected] (C. Li).

Abstract Antibiotics in wastewater are very harmful to environment and human health; their effective detection is important but still challenging. Herein, the first copper(I) iodine-based antibiotic sensor [Cu4I4(EBT)5] (denoted as UJN-Cu, EBT = 3-ethyl-1,3-benzothiazole-2-thione) was prepared through a facile solvothermal synthesis method and structurally determined by single crystal X-ray diffraction. The molecular structure of UJN-Cu adopts a chair-like structure of [Cu4I4(Ligand)5], which is distinctly different from the reported cubane- or chair-like [Cu4I4(Ligand)4] tetranuclear configurations. Theoretical calculations indicate that the greenish yellow fluorescent emission of UJN-Cu arises from the charge transition between the [Cu4I4] core and EBT ligand. The hydrophobic EBT as a shell of the [Cu4I4] core and the formation of three-dimensional supramolecular structure are responsible for the excellent stability of UJN-Cu in various antibiotic aqueous solutions. UJN-Cu behaves as a sensitive luminescence sensor for detection tetracycline hydrochloride (TCH) in aqueous system, and the limit of detection reaches as low as 10 µM. The obvious quenching effect of a tablet of UJN-Cu towards TCH at low concentrations can be obviously detected by naked eyes. Remarkably, the sensor is highly selective for TCH with quenching efficiency six times larger than other antibiotics, and can be reused for at least five cycles with the quenching efficiency nearly constant. This study not only represents the first copper(I) iodine cluster-based sensor for antibiotic detection, but also revealed molecular copper(I) iodine 1

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materials are of significance in monitoring water quality.

Keywords: Antibiotic detection, copper(I) iodine cluster, metal-organic supramolecular framework, Tetracycline

1. Introduction Tetracycline

hydrochloride

(TCH),

an

aromatic

molecule

with

an

octahydrotetracene-2-carboxamide skeleton, has been widely used as a pharmaceutical antibiotic in the treatment of human and animal infectious disease due to its broad-spectrum antimicrobial activity, excellent oral absorption, and low toxicity and cost.1 However, the misuse and abuse of them has brought about high levels of antibiotic residues in various aquatic environments including natural water systems, agricultural waste water streams, and even drinking water supplies, which not only generate increased drug resistance for microbial strains among mankind, but also produce allergic or toxic symptoms in some special individuals.2,3 An efficient antibiotic detection technology is extremely vital, not only before antibiotic residue removal, but also after antibiotic wastewater purification. The traditional methods to detect TCH include high-performance liquid chromatography, terahertz technology, surface plasmon resonance, capillary electrophoresis, etc. Most of these methodologies, however, require complicated sample handling procedure, highly skilled personnel or expensive instruments. Therefore, it is urgent to develop other convenient and cost-effective antibiotic detection methods. The optical sensing method that utilizes the changes of the luminescence signals caused by the interactions between sensor and analyte is superior in known detection methods, due to its easy operation, quick response, high selectivity and sensitivity.4,5 Recently, carbon-6-9 and silica-based quantum dots,10,11 and metal nanoparticles12,13 have been reported as luminescence sensors to detect TCH according to the mechanisms of inner filter effect (IFE) or charge transfer (CT). Whereas, most of the above sensors face the issues of tedious synthesis, slow response, relatively low sensitivity or selectivity etc.5 As a result, the exploration of new optical sensors with facile synthesis procedure, and effective detection of TCH in aqueous media is of practical significance.5,14 2


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Copper(I) iodine metal-organic clusters are of particular interest and constitute a large number of photoactive functional materials based on a relatively abundant, low cost and non-toxicity copper element.15-19 Due to their versatile coordination environments these compounds play a unique role in both photochemical and photophysical research and application, such as stimuli-responsive luminescence,20-26 solid-state lighting,18,27-31 etc. Accordingly, these compounds are also particular appealing for their application in antibiotic optical detection. However, copper(I) iodine-based antibiotic sensor has never been reported up to now, despite several zinc, zirconium or lanthanide metal-organic framework sensors have been reported recently.32-38 Tetranuclear copper(I) iodine clusters are in principle very promising candidates in this respect, due to their outstanding optical property which is highly sensitive to their solid-state organization via intermolecular interactions, and exhibit stimuli-responsive character.22,23,39-44 In this contribution, we report a novel tetranuclear copper(I) iodine metal-organic cluster [Cu4I4(EBT)5] (denoted as UJN-Cu, EBT = 3-ethyl-1,3-benzothiazole-2-thione), which assembled into a water-stable three-dimensional (3D) supramolecular framework. Notably, UJN-Cu represents the first reported copper(I) iodine-based antibiotic optical sensor with highly selective, sensitive and naked eye-visible luminescence detection of TCH in aqueous system.

2. Experimental section

2.1 Materials and characterization Cuprous iodide and 2-mercaptobenzothiazole were purchased from Macklin. Hydroiodic acid was purchased from Kefeng Chemical Regent Co., Ltd. Ethanol and acetonitrile were supplied by Sinopharm Chemical Regent Co., Ltd. Powder X-ray diffractions (PXRD) were conducted on a Bruker D8 Advance diffractometer with Cu-Kα radiation (λ = 1.541 Å). A Shimadzu UV-3101 spectrophotometer was used to get the optical diffuse reflectance spectra, with a BaSO4 plate as the standard (100% reflectance). The absorption spectrum was got from reflectance spectrum through the Kubelka-Munk function.45 The solid-state luminescence excitation and emission spectra were recorded on an Edinberg FLS920 fluorescence spectrophotometer at room temperature. The absolute emission quantum yield was also 3



obtained on Edinburgh machine with a calibrated integrating sphere as a sample chamber, and BaSO4 as a reflecting standard. X-ray photoelectron spectroscopy (XPS) analyses were measured on a ThermoFisher ESCALAB250 X-ray photoelectron spectrometer using Al-Kα radiation (λ = 8.357 Å). 2.2 Luminescence detection of antibiotics A home-made solid-state luminescent measurement system was employed to explore the luminescence detection of antibiotic (Figures 2d and S9).46,47 A tablet of UJN-Cu with a diameter of 5 mm and a thickness of about 1 mm was stick to a quartz plate, which was pushed into a quartz cell. Then the cell was positioned firmly in a phosphorimeter. During the experiments, the position of the measurement system was kept constant. A syringe with a long needle was used to add and remove water and different analytes. Each experiment was repeated at least three times to get a concordant value.

2.3 Theoretical calculation details The calculations toward UJN-Cu were based on its X-ray crystallographic data without optimizing the geometry. The density of states (DOS) as well as the optical absorption was calculated by density functional theory (DFT) with the CASTEP code,48,49 which employs a plane wave basis set for the valence electrons and norm-conserving pseudopotential for the core electrons.50 Pseudo-atomic calculations were conducted on Cu 3d104s1, S 3s23p4, I 5s25p5, C, 2s22p2, N 2s22p3 and H 1s1. The parameters and the convergence criteria were used the default values in the CASTEP code.48,49

2.4 Preparations of UJN-Cu A mixture of cuprous iodide (0.048 g, 0.25 mmol), 2-mercaptobenzothiazole (denoted as HBT, 0.042 g, 0.25 mmol), 45% hydroiodic acid (0.30 mL), ethanol (1.0 mL) and acetonitrile (5.0 mL) were sealed in a 25-mL Teflon-lined stainless steel vessel under autogenous pressure, which was heated at 140 °C for three days and finally slowly cooled down to room temperature. Yellow green block single-crystals of UJN-Cu were obtained as a pure phase with 19% yield (based on Cu). Elemental analysis calcd. (%) for C45H45N5S10Cu4I4: C 31.09, H 2.61, N 4.03; found: C 30.55, H 2.55, N 4.02. IR (KBr pellet, cm–1) 3068(vw), 3965(vw), 4


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2875(vw), 1452(s), 1378(vs), 1313(s), 1243(m), 1114(s), 1004(m), 914(m), 746(s), 536(vw). UJN-Cu is stable in air and insoluble in water, ethanol, acetonitrile and acetone. However, it is soluble in N, N-dimethylformamide (DMF). The PXRD measurement was employed to confirm the phase purity of crystals of UJN-Cu (Figure 4a). The experimental PXRD pattern matches well with the simulated pattern from the single-crystal structure, which indicates the phase purity of the bulk crystalline material.

2.5 Single crystal X-ray crystallography Crystal data of UJN-Cu was collected on an Xcalibur, Eos, Gemini diffractometer (Mo-Kα, λ = 0.71073 Å) at 293 K. The reduction of the data was performed by the CrysAlisPro program.51 The structure was solved by direct method and refined employing the Siemens SHELXL package of crystallographic software.51 The structural data was refined using a full-matrix least-squares refinement on F2. The non-hydrogen atoms were all refined anisotropically. The organic H atoms were located at geometrically calculated positions and refined as riding on their parent C atoms with Uiso(H) = 1.2Ueq(C). The Cu2 atom is divided into two different places (Cu2 and Cu2’) with the site occupancies both refined as 0.5. Accordingly, the EBT ligand attached to Cu2 atom was also refined with the occupancy as 0.5. The C21 atom was split into C21 and C21’ with the occupancies both refined as 0.5. The crystallographic data, structural refinements, important bond lengths and angles of UJN-Cu are summarized in Tables 1 and S1. Table 1. Crystal and Structure Refinement Data for UJN-Cu. UJN-Cu Formula

C45H45N5S10Cu4I4

Mr (g mol–1)

1738.22

Crystal system

Monoclinic

Space group

P21/c

ρcalcd [g cm–3]

2.081

a [Å]

9.1517(3)

b [Å]

14.9678(5)

5



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c [Å]

20.2748(6)

β [°]

92.976(3)

V [Å3]

2773.51(15)

Z

2

F(000)

1676.0

θ range [°]

3.23–25.35

Measured reflections

15523

Independent reflections (Rint)

5014 (0.0349)

Data/params/restraints

3252/348/45

R1a, wR2b [I>2σ(I)]

0.0568, 0.1315

Goodness of fit

1.030

∆ρmax and ∆ρmin [e Å–3]

0.617, –0.871

a

R1 = ∑||Fo|−|Fc||/∑|Fo|, bwR2 = {∑w[(Fo)2−(Fc)2]2/∑w[(Fo)2]2}1/2

3. Results and discussion

3.1 Structural description for UJN-Cu The crystal structure of UJN-Cu was determined by single-crystal X-ray diffraction (SXRD) study. The result shows that UJN-Cu crystallizes in the monoclinic P21/c space group and features a neutral chair-like [Cu4I4] core coordinated by five EBT molecules through covalent Cu–S bonds. The asymmetric unit contains two Cu(I) atoms, two I– ions and 2.5 neutral EBT ligands (Figure 1). The Cu1 atom lies in a typical tetrahedral geometry, which is coordinated by two µ3-I, one µ2-I, and one S atom to form a Cu1I3S tetrahedron. The other Cu atom is split into two different places (Cu2 and Cu2’) with occupancies both refined as 0.5. The Cu2’ atom is coordinated by one µ2-I, one µ3-I, and one S atom from an EBT ligand to form a Cu2’I2S plane triangle. Differently, each Cu2 atom is surrounded by one µ3-I, one µ2-I and two S atoms to form a Cu2I2S2 tetrahedron. As shown in Figure S2, the asymmetry unit connects with its symmetry-related one to form the molecular structure of UJN-Cu. Such non-centrosymmetrical molecules reside equimolarly with their opposite orientated molecules in the crystal lattice, as demonstrated in Figure 1. Each EBT ligand was 6


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formed from HBT molecule via in situ reactions. As shown in Scheme S1, the N-alkylation reaction introduces an ethyl on the thiazole N atom; meanwhile, the sulfydryl group was deprotonated and further coordinates to the neutral [Cu4I4] core via forming Cu–S bond.52,53 The Cu–I and Cu–S bond distances are in their normal ranges of 2.517(1) Å–2.785(1) and 2.234(1) Å–2.354(1) Å, respectively.31 The Cu1···Cu2’ distance of 2.684(1) Å is shorter than the sum of the van der Waals radii of Cu, suggesting there are Cu···Cu interactions in UJN-Cu. Via face to face π⋅⋅⋅π interactions within the aromatic rings of EBT ligands from different tetranuclear clusters, the tetranuclear clusters assemble into a 3D supramolecular framework as depicted in Figure S3. The crystal structure of UJN-Cu is unprecedented. Hitherto, the reported tetranuclear copper(I) iodine metal-organic clusters are all formulated as [Cu4I4(Ligand)4],15,16,22 where each cubane- or chair-like [Cu4I4] core are functionalized by four nitrogen or phosphine ligands, as shown in Scheme 1 (a-b). However, the molecular copper(I) iodine cluster reported here represents a chair-like [Cu4I4] core protected by five nitrogen/sulphur-based ligands generating two different coordinated terminal Cu atoms, which enriches the copper(I) iodine metal-organic cluster family (Scheme 1c).

Figure 1. (a) The molecular structure of UJN-Cu. Symmetry code: A (1–x, 2–y, 1–z). (b) The chair-like [Cu4I4] core in UJN-Cu with tetrahedral and plane triangular coordinated terminal 7



Cu atoms.

Scheme 1. The known tetranuclear copper(I) iodide clusters, referred as “cubane-like” (a) and “chair-like” isomers (b) respectively, which contain either tetrahedral or plane triangular coordinated terminal Cu atoms. (c) UJN-Cu represents a new tetranuclear copper(I) iodide structure.

3.2 Optical properties and mechanisms The optical properties in the solid state and their mechanisms were studied in detail. The photoluminescence (PL) property of HBT ligand and the solid state absorption spectra of UJN-Cu were provided in the Supporting Information (Figures S4-S5). As shown in Figure 2b, UJN-Cu has shown an obvious PL when irradiated with a 254-nm UV light. Naked eyes can easily distinguish the bright emission, which was photographed by a digital camera. Figure 2a indicates that upon irradiation of 400-nm light, the peak value and full width at half-maximum (FWHM) are 557 nm and 157 nm, respectively. At this point, the CIE coordinate and CCT value are (0.42, 0.51) and 3916, respectively, suggesting the emission of greenish yellow light (Figure 2b). The profile and peak of UJN-Cu remain nearly unchanged, although changing the excitation wavelength from 320 nm to 450 nm (Figure S5), suggesting the emission of UJN-Cu was wavelength-independent. The luminescent quantum yield at room temperature is 9%, which is comparable to that of cubane-like copper(I) iodine cluster with chiral phosphine as ligand (~ 8.7%),41 but lower than the majority of other cubane-like tetranuclear clusters.44, 54-56 However, it is still strong enough for UJN-Cu to act as a turn-off luminescence sensor. The lifetime of the 557-nm emission falls in the microsecond scale (9.13

µs), which are comparable with those reported for the cubane-like copper(I) iodide clusters, and also suggests the triplet state emission and phosphorescent character of UJN-Cu.57,58 8


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Figure 2. (a) The emission, excitation spectra of UJN-Cu (navy and dark yellow solid line, respectively) and the UV-vis absorption spectrum of TCH (orange dashed line). Lifetime (τ) for emissions at the positions marked with dashed lines are labeled. (b) The CIE chromaticity of UJN-Cu; (Insert): the optical images of UJN-Cu taken in ambient light and UV light. (c) The total and partial DOS of UJN-Cu. The Fermi level is set to zero by default. (d) The home-made luminescence sensor cell. A pressed tablet with diameter of 5 mm of UJN-Cu was stick to a quartz plate (1 mm × 8 mm × 50 mm) by acrylic AB adhesive. Then, the quartz plate was fixed on the inwall of a 1 cm suprasil cuvette by double faced adhesive tape.

To elucidate the PL mechanism of UJN-Cu, the density of states (DOS) and optical absorption were calculated based on the SXRD data using the CASTEP package (Figures 3 and S7). The calculated optical absorption curve is similar to the recorded UV-vis absorption; both show an obvious absorption in the region 300–600 nm with an obvious peak around 370 nm (Figure 3a). The highest absorption peak is predominantly contributed by the mixture 9



charge transfer from the separate state Sa to the Sb and Sc states. As shown in Figures 2c and 3b, The Sb and Sc states mainly include the p-π* anti-bonding orbitals of EBT molecule, while the Sa state mainly consists of the 3d state of Cu, 5p state of I as well as p-π bonding orbital of EBT ligand. Accordingly, the intrinsic absorption of UJN-Cu can be attributed to the charge transitions from I 5p state and Cu 3d state to p-π* orbitals of EBT ligand, as well as the intra-ligand charge transition. Considering that the location and profile of the emission spectrum of UJN-Cu are obviously different from those of the HBT molecule (Figure S4), the emission band centered at 557 nm for UJN-Cu was finally assigned to the charge-transfer triplet excited state between inorganic tetranuclear core and organic ligand (denoted as an IOCT mechanism).25,31

Figure 3. (a) Experimental and calculated optical absorption spectra for UJN-Cu. (Insert: the single crystals of UJN-Cu). (b) The total and partial DOS of UJN-Cu. Sa–c represent the maxima of the density of states in corresponding regions.

3.3 Luminescence sensing for antibiotics Considering the thermal and water stabilities of a material are very important for practical applications. The thermal stability under a N2 atmosphere and the water stability exposed to different analytes for UJN-Cu were investigated. The TGA curve shown in Figure S8 indicates that UJN-Cu remains stable up to ~142 °C. The PXRD patterns show that there are no structure transformations for UJN-Cu in water, even after successive exposure to different antibiotic aqueous solutions (Figure 4a). The high water stability of UJN-Cu could 10


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be explained by the following structural features. 1) Soft lewis acidic copper(I) bonds preferentially to soft lewis basic sulfydryl S-containing EBT ligand. As a result, the EBT shell could stabilize and protect the [Cu4I4] core well. 2) The ethyl group introduced by the in situ N-alkylation reaction could increase the hydrophobicity of EBT ligand, and further enhance the stability of the tetranuclear cluster. 3) The tetranuclear clusters further assemble into a stable 3D supramolecular framework in the crystal lattice of UJN-Cu.

Figure 4. (a) The PXRD patterns of UJN-Cu under different conditions. (b) Luminescence quenching of UJN-Cu by different analytes. (c) The emission spectra of UJN-Cu dispersed in aqueous solution of TCH with increasing concentration; Insert: The optical images taken under UV light for the tablet of UJN-Cu in H2O, 0.1, 0.5 and 1.0 mM TCH aqueous solutions. (d) Stern-volmer plot of UJN-Cu for TCH.

The excellent water stability as well as the good luminescent performance of UJN-Cu prompts us to study its optical detection properties in aqueous system. To do this, a home-made solid-state luminescent measurement system was employed here (Figures 2d and S9). The single crystals of UJN-Cu were well grinded and pressed into a 5-mm diameter 11



tablet, which was stick to a quartz plate and then fixed in a suprasil cuvette, as shown in Figure 2d. Note that such a solid-state luminescent measurement system is suitable for outdoor operation and easy to regenerate of the sensor, which only needs washing the tablet several times with distilled water in the quartz cell.46,47 The luminescence intensities of UJN-Cu soaked in water show different degrees of quenching upon contact with different analytes. Eight commonly used antibiotics such as tetracycline hydrochloride (TCH), tetracycline (TC), chloramphenicol (CMP), amoxicillin (AMX), ampicillin (AMP), ciprofloxacin (CIP), ronidazole (RDZ), sulfamethazine (SMA), and five common organic chemicals including p-Aminophenol (AP), bisphenol A (BP), o-Nitrophenol (o-NP), 1,4-Benzoquinone (BQ) and phenol as analytes were checked. Figure 4b shows the percentages of luminescence quenching according to introducing different analytes at room temperature. The quenching efficiencies of UJN-Cu exposed to these analytes are in the order of TCH > TC > CMP > AMX > AMP > CIP > RDZ > SMA for antibiotics group, and AP > BP > o-NP > BQ > phenol for organic chemicals group. Clearly, TCH as an analyte leads to the highest quenching efficiency of 26% at 1 mM, which is about six times larger than the efficiencies of other antibiotics (1 mM or saturated aqueous solutions, see Table S3), and three times larger than that of the saturated TC aqueous solution. Meanwhile, the quenching efficiencies of AP and MP chemicals are about three times larger than those of o-NP, BQ and phenol. Furthermore, the obvious quenching effect of UJN-Cu towards TCH under UV light can be obviously detected by naked eyes (Figure 4c, insert), however other antibiotics cannot. Such an obvious quenching effect towards TCH implies that UJN-Cu could be used as an easily distinguished “turn-off” sensor for detecting TCH by a spectrofluorometer or naked eyes. To study the sensing performance of UJN-Cu towards TCH, the luminescence intensities towards the incremental concentrations of the analyte were investigated. Figure 4c shows the luminescence intensity of UJN-Cu dispersed in TCH aqueous solution gradually decreased with the increasing concentrations. The Stern-volmer (SV) equation was used to quantitatively explain the luminescence quenching efficiency:59 I0/I = KsvC + 1, where Ksv is the quenching constant, M–1; C is the analyte concentration, i.e., the TCH in this study; I0 and

I represent the luminescence intensities with or without the analyte, respectively. As shown in 12


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Figure 4d, the SV plot for TCH concentrations displays a linear relationship in the whole test range of 0–3 mM, demonstrating that the SV equation can be used here. The calculated Ksv value of UJN-Cu for detecting TCH is 3.8×102 M–1. Accordingly, the limit of detection (LOD) of UJN-Cu for TCH detection was calculated to be ~ 4.8 ppm (10 µM) according to the formula of LOD = 3Sb/Ksv, where the Sb is the standard deviation (Table S4). This value is comparable with the reported value of 5.6 µM of metal Cu nanoclusters for detecting TCH.13 The recycling performance of UJN-Cu as a luminescence sensor toward TCH was also investigated (Figure S10). The result shows that UJN-Cu still can reach its initial luminescence intensity over five cycles, which demonstrates the excellent recyclability of UJN-Cu for its long-time in-field sensing application.

Figure 5. (a) A comparison of the quenching efficiencies of UJN-Cu exposed to mixed antibiotics (1 mM or saturated as shown in Table S3). (b) Time-resolved luminescence decay curves of UJN-Cu before and after the addition of TCH.

Considering the more realistic case, there are always mixed antibiotics in wastewater. Thus, the selective optical sensing of antibiotics in aqueous solution is more desirable. It has been demonstrated that UJN-Cu exhibits high quenching efficiency towards TCH, but very low towards SMA, RDZ, CIP and AMP. The selective detection experiments were performed as follows: the luminescence spectrum of UJN-Cu in 1 mM TCH was first recorded. Then, the freshly prepared mixed aqueous solution of TCH (1 mM) and another antibiotic (1 mM or saturated) was injected into the home-made measurement system. After each change of the solution, the emissions of UJN-Cu were measured. As shown in Figure 5a, an obvious 13



enhanced luminescence quenching was observed after the addition of TCH in the SMA, RDZ, CIP and AMP solution. Furthermore, we mixed SMA, RDZ, CIP and AMP solutions at the same volume as a more complicated analyte for luminescence detection. As can be seen, the complicated analyte only lead to a slight decrease of the luminescence intensity. However, upon introducing TCH into UJN-Cu and the mixed antibiotics system, the luminescence was obviously quenched. These results clearly indicate the high selectivity of UJN-Cu towards luminescence detection of TCH, in the presence of two or more other antibiotics. The PXRD and the XPS plots of UJN-Cu after the sensing experiments are almost the same as the corresponding plot of the as-synthesized UJN-Cu (Figures 4a, 6 and S11), suggesting the excellent stability of UJN-Cu as an antibiotic sensor. As a result, although some other methods have been employed to detect TCH and the LOD of UJN-Cu is not the lowest, however its easy operation, high selectivity and excellent recyclability made this method as a new and important approach to detect TCH.

Figure 6. XPS spectra of UJN-Cu at different conditions. Black line: as synthesized; navy line: after the sensing experiments. (a) Cu 2p, (b) I 3d, and (c) S 2p.

Generally, luminescence quenching may be through two different effects, 1) static quenching effect (SQE). The sensor and the quencher generate a non-luminescent complex, which quickly goes back to the ground-state without emitting photon when absorbs the light; 2) dynamic quenching effect (DQE). The excited-state sensor is non-radiatively deactivated when it collides with the quencher.59,60 The luminescence lifetime is the most definitive criterion to check which quenching mechanism worked in a quenching process. For SQE, the 14


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excited state lifetime keeps constant, while for a DQE case the lifetime ratio τ0/τ is close to the intensity ratio of I0/I. Figure 5b shows the luminescence decay curves of UJN-Cu before and after the addition of TCH. The luminescence lifetimes of UJN-Cu remain almost unchanged with or without TCH, which suggests the luminescence quenching observed for UJN-Cu should be mainly ascribed to SQE, rather than DQE. As demonstrated in Figure 2a, TCH possesses an obvious overlap region with the excitation spectrum of UJN-Cu, suggesting the quencher absorbs the excitation light of the sensor, which belongs to the IFE mechanism.61 Thus, both IFE and SQE mechanisms dominate the luminescence quenching of UJN-Cu in TCH solution.9,60 Moreover, the selectivity luminescence quenching toward TCH could also be explained by the IFE mechanism. As shown in Figure S12, TCH has a larger overlap with the excitation wavelength of UJN-Cu than other antibiotics, which leads to the highest IFE efficiency. The lower quenching efficiency of TC than TCH is ascribed to its lower solubility in water. A similar mechanism is also considered responsible for the selective luminescence quenching behavior of UJN-Cu towards the organic chemicals group (Figure S13).

4. Conclusion To conclude, we present the first copper(I) iodine-based sensor UJN-Cu for optical detecting antibiotic. The sensor was obtained through a facile solvothermal synthesis method, and contains a chair-like [Cu4I4] core and five N,S-based EBT as ligands, which represents a new member in the tetranuclear copper(I) iodine cluster family. The EBT ligand was formed via in-situ N-ethylation reaction and contributes greatly to the high water stability of UJN-Cu. DFT calculations indicate that the strong greenish yellow fluorescent emission of UJN-Cu mainly came from the charge transitions from [Cu4I4] core to EBT ligands. Significantly, UJN-Cu is highly sensitive and selective for TCH in water system with exclusively decreased luminescence emission as compared to other antibiotics, and the LOD was measured as 4.8 ppm. The luminescence quenching of the tablet sensor of UJN-Cu towards low concentration solutions of TCH can be obviously detected by naked eyes. The sensor can be reused for at least five cycles with the quenching efficiency remain nearly constant. Both IFE and SQE mechanisms dominate the luminescence quenching of UJN-Cu in TCH solution. The present 15



study not only represents a new and important approach to detect antibiotic TCH, but also revealed copper(I) iodine metal-organic clusters are of significance in monitoring water quality.

5. Acknowledgement We gratefully acknowledge the financial support by the NSF of China (21201080), the NSF of Shandong Province (ZR2017LB003, ZR2012BQ011), China Postdoctoral Science Foundation (177582), the Fund of State Key Laboratory of Structural Chemistry (20160016), and the science and technology project of University of Jinan (XKY1726) for financial support. The authors also thank Prof. G.-C. Guo, Dr. X.-M. Jiang, N.-N. Zhang and P.-Y Guo at Fujian Institute of Research on the Structure of Matter-CAS a lot for their help in physical property measurements.

6. Supporting Information. Electronic Supplementary Information (ESI) available: Electronic Supplementary Information (ESI) available: Crystallographic data, additional structural figures, TGA curve, IR, UV-vis absorption spectra of UJN-Cu and discussions, FL spectra of HBT ligand and discussion, recycling tests, and absorption spectra of antibiotics. Crystallographic data for UJN-Cu has been deposited in the Cambridge Crystallographic Data Centre (1827572). Author Contributions: All authors have given approval to the final version of the manuscript. Notes: The authors declare no competing financial interest.

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For Table of Contents Use Only A novel tetranuclear copper(I) iodide metal-organic cluster [Cu4I4(Ligand)5] with highly selective luminescence detection of antibiotic Guang-Ning Liu,*,a,b Ruo-Yu Zhao,a Rang-Dong Xu,a Xu Zhang,a Xue-Na Tang,a Qing-Juan Dan,a Yun-Wei Wei,a Yan-Yan Tu,a Qi-Bing Bo,a and Cuncheng Li*,a a

School of Chemistry and Chemical Engineering, University of Jinan, Jinan Shandong

250022, PR China b

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure

of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China

Reported here is the first highly selective and naked-eye-visible copper(I) iodine-based antibiotic optical sensor [Cu4I4(EBT)5], which exhibits a new type of copper(I) iodine tetranuclear structure.

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A novel tetranuclear copper(I) iodide metal-organic cluster [Cu4I4

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