Highly Selective Bifunctional Luminescent Sensor toward

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Highly Selective Bifunctional Luminescent Sensor towards Nitrobenzene and Cu2+ Ion Based on Microporous Metal– organic Frameworks: Synthesis, Structures, and Properties Li-Rong Yang, Chen Lian, Xuefei Li, Yuyang Han, Lele Yang, Ting Cai, and Caiyun Shao ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 03 May 2017 Downloaded from http://pubs.acs.org on May 3, 2017

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ACS Applied Materials & Interfaces

Highly Selective Bifunctional Luminescent Sensor towards Nitrobenzene and Cu2+ Ion Based on Microporous Metal–organic Frameworks: Synthesis, Structures, and Properties Lirong Yang*, Chen Lian, Xuefei Li, Yuyang Han, Lele Yang, Ting Cai, Caiyun Shao Henan Key Laboratory of Polyoxometalate, Institute of Molecule and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, P. R. China

ABSTRACT: Two metal-organic frameworks (MOFs), namely, [Ni(DTP)(H2O)]n (I) and

[Cd2(DTP)2(bibp)1.5]n

(II)

(H2DPT

=

4'-(4-(3,5-dicarboxylphenoxy)

phenyl)-4,2':6',4''-terpyridine, bibp = 1,3-di(1H-imidazol-1-yl)propane) have been solvothermally prepared, which present structural diversity. Single crystal X-ray diffraction analysis indicates that they consist of {NiN2O4} building units (for I), {CdO4N2} and {CdO3N3} building units (for II), which are further linked by multicarboxylate

H2DPT

to

construct

microporous

three-dimensional

(3D)

frameworks. The remarkable character of these frameworks is that coordination polymer II demonstrates highly selective and sensitive bifunctional luminescent sensor towards nitrobenzene and Cu2+ ion. The fluorescence quenching mechanism of II caused by nitrobenzene is ascribed to electron transfer from electron-rich (II) to electron deficiency nitrobenzene. The result has also been evidenced by the Density Functional Theory (DFT). Furthermore, antiferromagnetic as well as electrochemical characters of Ni-MOF (I) have also been investigated in this paper. KEYWORDS: metal-organic framework, solvothermal synthesis, fluorescent recognition, luminescence quenching, sensor INTRODUCTION Metal-organic frameworks, also being defined as microporosity-containing coordination polymers have aroused immense focal interests recently, which are built on the inherent strong coordination of the linkers to the metal centers, and this strong coordinative bond always contributes to form rigid, stable, crystalline functional materials amenable to applications development in many respects, such as gas storage or separation, molecular fluorescence sensor, magnetic properties, drug delivery, etc.1−10 Among diverse applications, fluorescence sensors closely related to luminescent MOFs are of great concern on account of their higher selectivity, sensitivity, and operability.11−16 1

ACS Paragon Plus Environment


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With rapid development of industry and the social activities of human beings, some heavy metal ions and toxic small molecules have been released，which have been serious threat to the environment and the health of human being.17-19 Sensing and detection of metal ions play a significant role in environmental and ecological system. Among them, Cu2+ ion is one of the essential ions in biological systems, which involves in diverse redox processes and enzyme functions, etc. What is more, many kinds of pigments are closely related to Cu2+ ion as cofactor. But, once exceeding maximum upper limit for copper consumption, can damage biomolecules to some extent. In fact, toxicity of Cu2+ ion brings about oxidative stress and correlative symptoms which may cause some Cu2+ ion metabolism disorders, such as neurodegenerative disorders and Wilson's disease etc.20−21 Nitrobenzene as the basic composition of explosives, can result in serious security problems, moreover, the high toxicity, nondegradable and accumulation characteristics make it harmful to health and environment. Therefore, looking out for a convenient and sensitive means to detect nitrobenzene at a low concentration is being the researcher’s focus, and recent years, the application of fluorescent MOFs in this respect has been reported.22−24 As is well-known, the properties of MOFs are highly dependent on their tunable microporous structures, and fluorescence quenching is normally achieved by the transfer of the excited electrons from MOFs to electron deficiency analytes.25−26 So, preselecting ligands with desired structural and geometrical information is a significant strategy in obtaining MOFs possessing targeted architectures and properties.27−29 Considering the above factors, we chose a large multidentate O/N ligand, 4'-(4-(3,5-dicarboxylphenoxy) phenyl)-4, 2':6', 4''-terpyridine (H2DPT) constructing sensing MOFs, which features as the combination of rigidity and flexibility, it comprises a flexible –O– group, in the process of crystallization, the phenyl ring could twist along the –O– group to match the coordination geometries of metal centers, and a tiny change in the orientation of a part of the ligand can cause significant changes in the characteristics of the pores.30−33 Herein we reported two 3D (three-dimensional) MOFs based on H2DPT and bibp (4'4-bis (imidazolyl) biphenyl): [Ni(DTP)(H2O)]n (I) and [Cd2(DTP)2(bibp)1.5]n (II). The luminescence studies show that coordination polymer II maybe acted as highly selective bifunctional luminescent sensor towards nitrobenzene and Cu2+ ion. EXPERIMENTAL SECTION 2


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Materials and Physical Measurements. All reagents in this work were commercially purchased and used without further purification. Infrared spectra (IR) were recorded from solid samples pelletized with KBr on a Nicolet 170 SXFT–IR spectrometer in the range of 400-4000 cm−1. The crystal structure was measured using a Bruker Smart CCD X-ray single-crystal diffractometer. Powder X-ray diffraction (PXRD) patterns were recorded on a Bruker D8 Advance instrument Cu-Kα radiation (λ =1.54056 Å) in the range of 2θ = 5-50° at room temperature. Electrochemical measurements were performed with RST5000F electro-chemical workstation with three-electrode setup. Magnetic measurement was measured by Quantum Design MPMS-XL SQUID magnetometer. Photoluminescence spectrum and lifetime were carried out on an Edinburgh FLS 980 analytical instrument equipped with 450 W xenon lamp and UF900H high-energy microsecond flashlamp as the excitation source. The thermogravimetric analysis (TGA) was performed using a NETZSCH STA449F5 thermogravimeter. The heating rate was programmed as 10 K·min−1 with the protecting stream of N2 flowing of 40 mL·min−1. Synthesis of [Ni(DTP)(H2O)]n (I). A mixture of 4'-(4-(3,5-dicarboxylphenoxy) phenyl)-4,2':6',4''-terpyridine (24.5 mg, 0.05 mmol), 1,3-di-(1H-imidazol-1-yl) propane (8.8 mg, 0.05 mmol), Nikel perchlorate hydrate (27.4 mg, 0.075 mmol) and 8 mL DMF-water (v / v=1:3) was mixed by stirring for 30 min, the pH value of the mixture solution was adjusted to 4.0 by dropwise adding NaOH solution (1 mol·L-1), then transferred into 25 mL Teflon-lined stainless steel autoclave at 150 ℃ for 72 h. The reaction system was cooled to ambient temperature at a rate of 5 ℃ / h, then blocky green crystals were obtained. Yield of 78.53% (based on Nikel perchlorate hydrate). IR data (KBr, cm-1): 3393(br), 1613(m), 1601(m), 1552(s), 1510(m), 1466(m), 1406(s), 1369(s), 1320(w), 1251(s), 1225(m), 1177(m), 1064(w), 976(m), 827(s), 779(m), 724(s), 710(w), 686(w), 650(w), 590(w), 522(m). Synthesis

of

[Cd2(DTP)2(bibp)1.5]n

(II).

A

mixture

of

4'-(4-(3,5-

dicarboxylphenoxy) phenyl)-4, 2':6', 4''-terpyridine (36.7 mg, 0.075 mmol), 4'4-bis(imidazolyl) biphenyl (21.5 mg, 0.075 mmol), Cadmium perchlorate hydrate (32.2 mg, 0.075 mmol) and 8 mL DMF-water (v / v = 1:3) was mixed and stirred for 30 min, the pH value of the solution was kept at 5.7 by addition of NaOH solution (1 mol·L-1). Under similar conditions, blocky light yellow crystals were collected. Yield of 58.33% (based on Cadmium perchlorate hydrate). IR data (KBr, cm-1): 3417(br), 1607(s), 1556(s), 1513(s), 1453(w), 1396(m), 1364(m), 1244(s), 1128(w), 1177(w), 3



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1109(w), 1065(m), 1014(w), 963(w), 827(s), 779(w), 778(w), 729(m), 625w), 638(w). Crystallographic Data Collection and Refinement. Single-crystal diffraction data of I and II were collected on a Bruker Smart CCD X-ray single-crystal diffractometer with graphite monochromated MoKα-radiation (λ = 0.71073 Å). All independent reflections were collected in a range of 3.12-26.37º for I, and 1.06-28.31º for II. Multi-scan empirical absorption corrections were performed using SADABS. Direct methods were used to solve crystal structures. Positional and thermal parameters were refined by the full-matrix least-squares technique on F2 using the SHELXTL package. The detailed crystallographic data are summarized in Table 1. Selected bond lengths and bond angles for the coordination polymers I and II are given in Table S1. CCDC 1460855 and 1460854 correspond to I and II, respectively. Table 1. Summary of crystallographic data for I and II. compound

I

II

Empirical formula Formula weight Temperature / K Crystal system Space group a/Å b/Å c/Å α / (°) β / (°) γ / (°) Volume / Å3 Z ρcalcg / cm3 µ / mm-1 F (000) Crystal size / mm3 Radiation 2θ range for data collection/° Index ranges

C29H19N3NiO6 564.16 293(2) orthorhombic Ibca 19.6682(6) 25.9267(10) 23.5206(10) 90.00 90.00 90.00 11993.9(8) 16 1.250 0.690 5440 0.44 × 0.38 × 0.24 MoKα (λ = 0.71073) 6.24 to 52.74 -24 ≤ h ≤ 24, -30 ≤ k ≤ 32, -29 ≤ l ≤ 28 26149 6121 [Rint = 0.0396, Rsigma = 0.0407] 6121 / 0 / 353 1.065

C85H55Cd2N12O10 1629.23 296.15 triclinic P -1 10.5207(6) 19.5694(11) 19.8195(12) 85.5670(10) 76.2310(10) 85.8780(10) 3945.4(4) 2 1.371 0.605 1650 0.34 × 0.26 × 0.22 MoKα (λ = 0.71073) 2.12 to 56.628 -13 ≤ h ≤ 13, -26 ≤ k ≤ 18, -24 ≤ l ≤ 25 25242 18194 [Rint = 0.0277, Rsigma = 0.0740] 18194 / 75 / 1013 1.017

Reflections collected Independent reflections Data/restraints/parameters Goodness-of-fit on F2

4


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Final R indexes [I > 2σ (I)] Final R indexes [all data]

R1 = 0.0396, wR2 = 0.1206 R1 = 0.0572, wR2] = 0.1288

R1 = 0.0513, wR2 = 0.1329 R1 = 0.1002, wR2 = 0.1720

RESULTS AND DISCUSSION Structural Description of I and II. [Ni(DTP)(H2O)]n (I). The single-crystal X-ray diffraction analysis reveal that I crystallizes in an orthorhombic crystal system with the space group Ibca. The coordination environment of Ni(II) center is six-coordinated using three carboxylic O atoms belonging to two independent DTP2ligands, one water O atom, as well as two N atoms deriving from another two DTP2ligands to fabricate a distorted octahedral configuration containing a {NiN2O4} moiety (as illustrated in Figure 1a). The DTP2- carboxylate anion displays µ4-(η2-O, O’), O’’, N, N’’ coordination mode (mode a, for details see Scheme 1). The Ni–O bond lengths vary from 2.0062(15) to 2.1727(16) Å, and bond distances of Ni–N lie in the range of 2.071(2)-2.109(2) Å, which are in agreement with those in reported researches concerning Ni(II) complexes.34−36 In coordination polymer I, the adjacent {NiN2O4} units are connected each other to generate infinite wavy chains (see Figure 1c). These chains are bridged covalently to construct a 2D layer with the channels with the dimension of 19.4382 × 14.2392 Å2 (defined by the atom-to-atom distance of the opposite angles) (Figure 1b). Based on these 2D sheets, coordination polymer I is further connected reciprocally along c-axis to generate a 3D neutral architecture (as shown in Figure 1d).

Figure 1. (a) Coordination environments of Ni(II) center in I. (b) 1D-channel-containing 2D architecture in I. (c) The 1D wavy chain in I. (d) The interpenetrated network topology of I. 5



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[Cd2(DTP)2(bibp)1.5]n (II). Coordination polymer II crystallizes in the triclinic crystal system with the space group P-1. Coordination polymer II involves in two Cd(II) ions. Each Cd(II) ion exhibits a distorted octahedral environment. The Cd(1) ion coordinates with four O atoms of carboxylic groups coming from two DTP2-, two N atoms from another DTP2- and one bibp linker in anti-form to form a {CdO4N2} unit (Figure 2a). Among the three molecules of DTP2-, one adopts µ3-(η2-O, O’), (η2-O’’, O’’’), N coordination mode (mode b) and two adopt µ3-(η2-O, O’), (η1-O’’), N mode (mode c) (see Scheme 1). On the other hand, the coordination environment around Cd(2) consists of a {CdO3N3} unit. The Cd(2) ion coordinates with three carboxyl O atoms of two DTP2- (mode c), one N atom from DTP2- (mode b) and two N atoms originating from bibp linkers (see Figure 2a). The bond distances of Cd–O lie in the range of 2.181(4)-2.617(4) Å, and those of Cd–N are of 2.267(4)-2.389(4) Å, which are consistent with corresponding values in previously reported references. 37−39 What is worth mentioning is that both types of units ({CdO4N2} unit for Cd(1) and {CdO3N3} unit for Cd(2)) are connected by two DTP2- in coordination mode b and c to build a binuclear motif. The neighbouring motifs are linked by two DTP2ligands in mode b and c, forming a 1D infinite ribbon (see Figure 2b). The 1D ribbons are parallel each other and the distance between adjacent ribbons is about 18.0949(9) Å. Based on the linkers of bibp, all the ribbons are connected to fabricate into a 2D layer (see Figure 2c). Adjacent layers are further packed into a 3D porous skeleton through covalent bonds as well as the π–π interactions between the partially overlapping aromatic rings of DTP2- or bibp ligands (see Figure 2d).

6


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Scheme 1. Coordination modes in I-II.

Figure 2. (a) Coordination environments of Cd(II) center in II. (b) 1D ribbon in II. (c) 2D layer in II. (d) 1D-cavity-containing 3D architecture in II. (e) The interpenetrated network topology of II.

Luminescent Properties of I and II. Luminescent properties of cadmium compounds based on various π-conjugated organic ligands have been inspiring the great attention owing to their promising applications in the aspects of chemical sensors. In the present work, the fluorescence properties of coordination polymers I-II together with the free H2DPT ligand were measured in solid state at ambient temperature, as depicted in Figure 3a. The fluorescence emission and excitation values of H2DPT are at 542 nm (λex = 370 nm), which attributes to the transition course from the lowest excited singlet state to the singlet ground state. The strong emission spectra of I and II are located at 491 and 520 nm (λex =370, 404 nm), respectively, exhibiting blue-shifted with the wavelengths of 51 and 22 nm compared to free H2DPT ligand, which may be ascribed to the perturbation brought about by coordination interaction of the ligand with the coordinated metal centers, the rigidity versus flexibility of the organic ligands and their di℃erent architectures.25, 7


40−42


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Furthermore, the fluorescence decays of the ligand H2DPT and coordination polymers in the solid state at ambient temperature are fitted into double-exponential decay laws with the following formula: I = A1 exp(t / τ1) + A2 exp(t / τ2), where τ1 and τ2 are defined as the fast and slow components of the luminescence lifetimes, while A1 and A2 denote the pre-exponential factors.43−44 The fitted fluorescence lifetimes τ1 and τ2 are 1.07 µs (45.48 %) and 9.48 µs (54.52 %) for the free ligand H2DPT, 0.92 µs (59.66 %) and 9.34 µs (40.34 %) for I, 0.85 µs (44.74 %) and 9.20 µs (55.26 %) for II. As a result, the average decay times (τ*) may be determined by the equation as follow: τ* = (A1τ12 + A2τ22) / (A1τ1 + A2τ2), giving the corresponding average lifetimes of 5.65 µs, 5.45 µs and 4.38 µs, respectively, which are shorter than that of the emissions caused by the triplet state (>10-3 s), thus emissions may result from a singlet state.45 In addition, lifetimes of I and II are shorter than the free ligand H2DPT which is mainly due to the increasing efficiency of nonradiative pathways (see details in Figure 3b-3d).46−47

Figure 3. (a) The emission spectra of H2DPT, I and II in solid state at room temperature. (b), (c) 8


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and (d) Luminescence decay curves of ligand H2DPT, I and II.

Detection of Metal Ions. The strong emissions of coordination polymer II impelled us to explore its luminescence sensing characteristics. The grounded powder samples of II was immersed in equal volumes of different DMF solutions containing 10−3 M of M(Cl)x (M =Li+, Ca2+, Ba2+, Co2+, K+, Na+, Cu2+ , Mg2+, Cd2+, Zn2+, respectively) for luminescence studies at ambient temperature. Emission spectra of II (λex = 306 nm) are illustrated in Figure 4. Intensity of emission spectra at 347 nm only show minor changes when LiCl, CaCl2, BaCl2, CoCl2, KCl, NaCl, MgCl2, CdCl2, ZnCl2 are introduced, respectively. While the emission spectrum containing CuCl2 presents obvious fluorescence quenching phenomenon, the intensity of which reduces sharply from 1699 a.u. to 2 a.u. compared to that without adding. This result indicates that II can detect Cu2+ ion efficiently through fluorescence quenching. Comparably, MOFs based on lanthanide metals presenting metal ion-centered luminescence, while those based on transition metals with d10 electronic configuration demonstrate ligand-based emissions more commonly, involving ligand-localized emission caused by π→π* and / or n→π* transitions of conjugated ligands, as well as ligand-to-metal charge transfer (LMCT) and metal-to-ligand charge transfer (MLCT).48 Broad emission at 347 nm of as-synthesized Cd-based coordination polymer II (excited at 306 nm) is attributed to intraligand π→π* and n→π* transitions and LMCT.

Figure 4. (a) Emission spectra of II in diverse metal ions. (b) Comparisons for intensities of II in different metal ions.

The framework of II was monitored by PXRD, IR spectra and TGA measurements. PXRD patterns revealed that the 3D framework of II did not collapse 9



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after sensing of NB or Cu2+ ion compared to that of the initial coordination polymer II (Figure S3). IR spectra indicated that the spectra of II after sensing of NB or Cu2+ ion are in good accordance with that of II (see Figure S4). The thermogravimetric analysis data demonstrated that the as-synthesized II was stable up to 356 ℃ (as illustrated in Figure S5). As mentioned above, the stability of framework for II demonstrates the feasibility of coordination polymer II as a luminescence sensor in DMF or DMA solutions. Sensing of Organic Small Molecules. Solid sample was respectively dispersed in different organic solvent, including methanol, acetone, acetonitrile (CH3CN), DMA, DMF, DMSO, toluene, benzene and nitrobenzene (NB). These results indicate that the luminescence of coordination polymer II largely depends on solvent molecules, especially at the existence of NB, which presents distinct fluorescence quenching. Meanwhile, DMA suspension of II showed the strongest emission band at ambient temperature. Therefore, the fluorescent detection experiments were performed in DMA solution. Emission spectrum of II at 346 nm (excited at 306 nm) in DMA is illustrated in Figure 5a. In order to investigate the sensitivity of fluorescence quenching character for NB further, emissive response was recorded by gradually increasing the concentration of NB in the suspension of coordination polymer II dispersed in DMA. The quench efficiency is defined as (Io-I) / Io × 100% (where Io denotes original fluorescence intensity of II, while I means fluorescence intensity of II after the introduction of the analyte). Figure 5b expounds the change of fluorescence quenching efficiencies upon increasing concentration of NB. The fluorescent intensity reduced up to 34.1% at the concentration of 60 ppm NB, and the quench efficiency reaches as much as 99.8% with increasing the concentration of NB to 300 ppm, indicating that II is sensitive in detecting trace quantity of NB.

10


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Figure 5. (a) Emission spectra of II in diverse analytes; (b) Emission spectra of II in DMA with different concentrations of NB.

In addition to evaluate its high sensitivity, the anti-interference ability of coordination polymer II as sensor is crucially significant. The effects caused by organic solvents on anti-interference ability of II are experimented. Fluorescence intensities of II dispersed in DMA were not reduced distinctly even if the introduction of a relatively higher concentration of analytes (1000 ppm). Whereas, with the introduction of 300 ppm NB in the parallel tests, the fluorescence intensities decreased sharply and presented obvious quenching phenomenon, and this excellent anti-interference ability make it possible for sensing in complicated compounds (see Figure 6). The blank experiment with the suspension of the ligand + DMA + NB has been performed. Consequently, the suspension did not cause the quenching, indicating that compound II acts as the crucial role in the course of quenching (for details see Figure S6).

11



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Figure 6. Fluorescence intensity of compounds in DMA with the introduction of diverse solvents (blue) and introduction of NB (red).

Theoretical Studies. In order to illuminate the nature of the high selectivity of II for NB, the mechanism of fluorescence quenching was investigated. Because of the limitations of the pore size caused by the interpenetration in the 3D framework of II, the fluorescence quenching phenomenon observed can be ascribed to the photoinduced electron transfer from the excited state of II to the electron deficiency NB which belongs to the surface adsorption.49−54 This type of surface adsorption may be beneficial to orbital overlapping between the acceptors and the donors. Conjugated MOFs are usually favourable electron donors and their abilities are reinforced by delocalized π* excited state, which may accelerate exciton migration and intensify the electrostatic interaction between the MOFs and electron deficiency molecules.55 As for MOFs, although they usually present outspread network frameworks, they are characterized by narrow energy bands due to their localized electronic states in most cases, especially for those MOFs containing d10 metal ions.56 In view of this, the MOFs may be known as giant “molecules” and the valence-band (VB) and conduction-band (CB) energy levels may be depicted similarly to molecular orbitals.53-54 Generally, energy levels of CB in MOFs are higher than those in the LUMOs of analytes, which may provide potent driving forces for electron transferring from electron-rich MOFs to electron-deficient analytes, and consequentially quenching the fluorescence intensity of MOFs upon excitation.57 Particularly for those electron-withdrawing-group containing molecules as nitroaromatics. Based on conjugation, the LUMOs of nitroaromatics are low-lying π* orbitals which are 12


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stabilized by −NO2 substituent, and their orbital energies are always lower than the CB of MOFs.58−59 From the above, the photoluminescence character of II (Cd-MOF) may be assigned to ligand-centered. Figure 7 exhibits the HOMO and LUMO energy levels of ligand and the selected analytes including NB, as calculated using DFT at B3LYP/6-31+G(d) level by employing Gaussian 03 package.60 The LUMO energy of the electron-rich ligand was calculated to be −2.51 eV, and is higher than that of NB (−2.91 eV) and lower than those of other tested analytes, which indicate that the excited state electrons transfer from electron-rich II to electron deficiency NB, and thus luminescence quenching effect may take place effectively.61−62 This quenching mechanism has been confirmed for conjugated MOFs and was evidenced here for II (Cd-MOF) of our HOMO and LUMO orbital energies and band structure calculations.63−64 This type of electron transfer process based on energy-dependent driving force is considered to be a significant role for the fluorescent sensibility to nitroaromatics. Simultaneously, the microporous structure of II and the internal surface furnish the adequate recognition sites and diffusion routes within its 3D framework which may facilitate the host–guest interaction between II and tested organic molecules, presenting higher sensitivity of sensing towards certain nitroaromatics.65

Figure 7. HOMO and LUMO energy levels of ligand and the selected analytes.

Electrochemical Properties. To survey the electronic properties of coordination polymer I, the cyclic voltammetry (CV) experiments of I bulk-modified glassy carbon electrode (GCE) were carried in 0.1 M KOH aqueous solution. The cyclic 13



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voltammograms of I-GCE at diverse scan rates are shown in Figure 8. It is obvious that a quasi-reversible redox peak is observed at the I-GCE in the range of 800 to 100 mV, which could be ascribed to the redox couple of Ni(III) / Ni(II). What's more, some reported metal organic complexes based on Ni (II) ions had shown different electrochemical properties, which might be due to the finally diverse structures and the various coordination modes of Ni(II) ions with organic ligands.66−67 Effect of scan rates on the electrochemical characteristics of I has been considered in various scan rates as the aforementioned conditions. When the scan rates increasing from 60 to 200 mVs−1, the cathodic peak potentials slightly decline to the negative direction, while the anodic peak potentials gradually raise to the positive direction. The diagrams of peak current versus square root of scan rates are shown in Figure 8. Peak currents of anodic and cathodic are proportional to the scan rates, indicating that the redox process for coordination polymer I is surface-controlled.

Figure 8. Cyclic voltammograms of I-GCE in 0.1 M KOH aqueous solution at diverse scan rates: 60, 80, 100, 120, 140, 160, 180, 200 mV s−1 (from inner to outer). The inset illustrates the linear relationship between peak currents versus scan rates.

Magnetic Studies. The variable temperature magnetic susceptibility data for coordination polymer I was investigated at 1000 Oe in the range of 2 to 300 K. The plots of χMT and χM versus T are shown in Figure 9a. The χMT value is 1.51 cm3mol−1K at 300 K, which is the order expected for single Ni(II) ion (s =1, g > 2.0).68 The χMT values decrease reposefully from room temperature to 20 K, then the 14


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χMT value sharply decreases to 0.65 cm3mol-1K at 2 K upon cooling, which exhibits the behavior of antiferromagnetic exchange interactions between Ni(II) ions. The temperature-dependent character of the reciprocal susceptibility χM−1 versus T of I obeys the Curie–Weiss law in the 300 K–2 K range (Figure 9b), giving C = 1.48 cm3mol-1 K, θ = −5.9 K, which further demonstrates antiferromagnetic interactions between magnetic centers. These phenomena verify the existence of the antiferromagnetic interaction and the carboxyl groups adopt coordination mode to metal centers, which may be contributed to the transport of antiferromagnetic coupling interactions.69−70

Figure 9. (a) Thermal variation of χM and χMT for I. (b) Plot of thermal variation of χM-1 for I.

CONCLUSIONS Summarily,

we

have

successfully

synthesized

two

MOFs,

namely,

[Ni(DTP)(H2O)]n (I) and [Cd2(DTP)2(bibp)1.5]n (II) using a new electron-rich dicarboxylic acid ligand H2DPT under solvothermal conditions. I shows antiferromagnetic and electrochemical properties. Remarkably, Cd-MOF II presents highly sensitive and selective towards nitrobenzene, and may be acted as a promising sensor for its rapid detection. The fluorescence quenching mechanism is the result of the electron transfer from electron-rich Cd-MOF to electron deficiency NB, and has also been evidenced by Density Functional Theory. Simultaneously, II shows significant fluorescence quenching effect upon the introduction of Cu2+ ion. Both luminescent experiments demonstrate that II is capable of highly selective detection of different types of analytes (NB and Cu2+ ion) through fluorescent quenching. The work reported here provides a helpful perspective for the design of sensitive fluorescent recognition sensors with multifunctional applications. 15



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ASSOCIATED CONTENT Supporting Information X-ray crystallographic file (CIF), selected bond lengths and band angles for coordination polymers I and II, PXRD patterns, luminescence decay curves, thermogravimetric analysis curve, and Emission spectra. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. (L. Yang) Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS This research is financially supported by the Natural Science Foundation of Henan Province of China (No. 162300410010 and 13A150056). REFERENCE (1) Venna, S. R.; Carreon, M. A. Highly Permeable Zeolite Imidazolate Framework-8 Membranes for CO2/CH4 Separation. J. Am. Chem. Soc. 2009, 132 (1), 76–78. (2) Horcajada, P.; Serre, C.; Maurin, G.; Ramsahye, N. A.; Balas, F.; Vallet-Regi, M.; Férey G. Flexible Porous Metal-Organic Frameworks for a Controlled Drug Delivery. J. Am. Chem. Soc. 2008, 130 (21), 6774–6780. (3) Canary, J. W.; Mortezaei, S.; Liang, J. Transition Metal-Based Chiroptical Switches for Nanoscale Electronics and Sensors. Coord. Chem. Rev. 2010, 254 (19), 2249–2266. (4) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The Chemistry and Applications of Metal–Organic Frameworks. Science 2013, 341 (6149), 1230444. (5) Seo, J. S.; Whang, D.; Lee, H.; Im Jun, S.; Oh, J.; Jeon, Y. J.; Kim K., A Homochiral Metal–Organic Porous Material for Enantioselective Separation and Catalysis, Nature 2000, 404 16


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Highly Selective Bifunctional Luminescent Sensor toward

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