Multiple Detection Characteristics of Two Zinc-phosphonates

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Multiple Detection Characteristics of Two Zinc-phosphonates: Syntheses, Crystal Structures and Luminescent Properties Hao-Hao Liu, Jie Pan, Zhen-Zhen Xue, Song-De Han, Jin-Hua Li, and Guo-Ming Wang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00800 • Publication Date (Web): 12 Aug 2019 Downloaded from pubs.acs.org on August 13, 2019

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Crystal Growth & Design

Multiple Detection Characteristics of Two Zinc-phosphonates: Syntheses, Crystal Structures and Luminescent Properties Hao-Hao Liu,† Jie Pan,† Zhen-Zhen Xue,† Song-De Han*,†, Jin-Hua Li† and Guo-Ming Wang*,†,‡ †College

‡Key

of Chemistry and Chemical Engineering, Qingdao University, Shandong 266071, P. R. China

Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou

University, Shantou, Guangdong 515063, P. R. China Supporting Information ABSTRACT: A couple of metal phosphonates, {[(CH3)2NH2][Zn2(HEDP)(BPDC)0.5(H2O)2]·H2O} (1) and {[CH3NH3][Zn2(HEDP)(BPDC)0.5(H2O)2]·3.5H2O} (2) (HEDP = 1-hydroxyethylidene diphosphonate, H2BPDC = biphenyl-4,4'dicarboxylic acid), have been successfully synthesized by virtue of the dual-ligand strategy. Both the Zn(II) centers in 1 and 2 are bridged by the -PO3 units of HEDP to form 2D inorganic-organic hybrid layers. Adjacent Zn-HEDP layers are further pillared and connected by the linear O-containing linkers to furnish the 3D pillared-layer architectures showing a (3,4)-connected network. Solid-state photoluminescence for compounds 1 and 2 have been performed, displaying the intense emission at 335 and 340 nm under UV light irradiation, respectively. Moreover, luminescence sensing experiment suggests that compound 1 exhibits a great selectivity and sensitivity for detection of Cu2+/Fe3+, IO4-/Cr2O72- and nitrobenzene, which could be considered as a promising multiple sensor in an aqueous system.

INTRODUCTION As a class of inorganic-organic hybrids, metal phosphonates represent a particularly important field due to not only their diverse architectures but promising properties as functional materials in the domains of photochemistry, catalysis, ion exchange, molecular magnetism, proton conductivity and so on.[1-9] Generally, the desirable solids fabricated by diverse phosphonates and various metal centers (main groups, transition metals, lanthanide ions, etc) could be equipped with several interesting merits: (a) the phosphonate molecules with multiple potential coordination sites enable them bridge several metal centers via diverse coordination modes; (b) the phosphate groups could adopt various fashions such as the neutral or anionic forms according to the pH values of the reaction system; (c) the targeted metal-phosphonate materials are usually robust and stable in air or water, thus could be considered as a significant advantage than other coordination polymers (CPs) in terms of practical application.[10-16] Numerous efforts have been continuously paid on the assembly of versatile metal phosphonates, leading to the important generation of crystal engineering. For instance, by employing a tetravalent zirconium ion as the metal nodes, Wang et al prepared a series of water-stable Zr-phosphonates which display high permanent porosity and exhibit excellent uranium uptake capabilities.[17] The porphyrin-based tetraphosphonic acid was used to assist the generation of the thermally and chemically stable metal-organic frameworks with proton conduction properties.[18] Zheng and co-workers reported a decanuclear dysprosium phosphonate, showing an interestingly reversible on-off switching of single-moleculemagnetism behavior.[19] In a word, the investigation of metal phosphonates with fascinating structures accompanied with excellent physicochemical properties is still a hot topic and

remains popular. A review of reported literatures on metal-phosphonate system reveals that novel architectures may be expected through the introduction of diverse ionic guest organic molecules as the templates or various organic linkers with different types and shapes as the auxiliary ligands during the assembly process.[20] With regard to the latter which is called the dual-ligand strategy, the N-containing molecules such as pyridine, imidazole, triazine, triazole together with their derivatives, are of particular interest when serving as the second building moieties to contribute the acquisition of final metal phosphonate products.[21-28] As the π-conjugated nitrogen-based ligands are usually regarded as electronacceptor once coordinated to various metal centers, and the phosphonate subunits could be served as the electron-donor, therefore the combination of these two different parts could give rise to a great deal of optimized photochromic hybrid materials.[29] Our group has paid many efforts on the construction of crystalline photochromic materials through the marriage of pyridine-derivative unit and Zn-phosphonate followed by the ligand-to-ligand charge transfer (LLCT) mechanism.[30-31] In addition, it has been widely acknowledged that the polycarboxylate ligands with multiple bridging modes through coordinated-O atoms are the great choice to act as the coligands for the generation of intriguing networks.[32-35] As a result, a large number of CPs possessing captivating architectures and attractive properties have thus been successfully constructed, which may be good candidates as functional hybrids in optics, electrics and magnetics.[36-41] However, the investigation of metal phosphonates with incorporated O-donor linkers is relatively less compared with the extensively reported pyridine- or azole-based metalphosphonate system, thus much more attention should be paid and attached.

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Table 1. Crystal and refinement data for solids 1 and 2.

As an our continuous work on metal phosphonates, we are employing the possibility to introduce the polycarboxylate linkers into metal-1-hydroxyethylidenediphosphonate (HEDP) system to hunt for new functional crystalline materials based on the following considerations: (a) the HEDP could adopt different chelating-bridging modes thus results in diverse networks; (b) the π-conjugated O-donor ligands could endow the final targets with good photoluminescence performance; (c) the high stability and rich host-guest chemistry of metal phosphonates are an ideal platform as chemical sensor.[42-45] Herein, we reported two isostructural Zn-phosphonates, {[(CH3)2NH2][Zn2(HEDP)(BPDC)0.5(H2O)2]·H2O} (1) and {[CH3NH3][Zn2(HEDP)(BPDC)0.5(H2O)2]·3.5H2O} (2) (H2BPDC = biphenyl-4,4'-dicarboxylic acid) with BPDC as the auxiliary ligands. The linkage of Zn(II) and HEDP firstly generates the 2D layered networks, and these neighboring layers are further linked through the linear O-containing ligands which act as the pillars, giving rise to a final 3D framework. The luminescent properties for both compounds were investigated. Moreover, luminescent sensing experiments indicate that 1 can act as a multiple sensor towards different ions and solvents.

Compounds Formula Mr (g

Materials and General Methods. All reagents have been bought and used without further purification. With the help of a Philips X’Pert-MPD diffractometer equipped with Cu-target tube, the powder X-ray diffraction (PXRD) spectroscopy has been performed. Elemental analysis for C H N data was collected from a Perkin-Elmer 240C analyzer. By employing a MAGNA-560 FT-IR spectrometer, we have carried out the IR spectroscopy. With a FLS920 spectrophotometer, the photoluminescence spectra could be obtained. Synthesis of {[(CH3)2NH2][Zn2(HEDP)(BPDC)0.5(H2O)2]·H2O} (1). 0.16 g ZnO (1.0 mmol), 0.12 g H2BPDC (0.5 mmol), 0.2 mL HEDP (1.6 mmol), 0.2 mL HF, 5 mL H2O and 5 mL DMF were mixed in a Teflon-lined autoclave with a volume of 20 mL, then the content was heated and kept at 145 °C for one week. As the temperature was decreased to 30 °C at a rate of 0.1 °C/min, colorless X-ray-quality crystals could be acquired with 58% yield based on H2BPDC. EA(%): calcd for C11H22NO12P2Zn2 (552.97): C, 23.89; H, 4.01; N, 2.53. Found: C, 23.98; H, 4.06; N, 2.64. IR (KBr pellets, cm-1): 3386 (s), 3050 (s), 2797 (s), 2493 (m), 1600 (s), 1539 (m), 1401 (s), 1108 (s), 990 (s), 935 (m), 812 (w), 764 (m), 675 (w) (Figure S2). Synthesis of {[CH3NH3][Zn2(HEDP)(BPDC)0.5(H2O)2]·3.5H2O} (2). A mixture of 0.16 g ZnO (1.0 mmol), 0.12 g H2BPDC (0.5 mmol), 0.15 mL HEDP (1.2 mmol), 0.2 mL HF, 10 mL H2O and 0.8 mL methylamine was placed and sealed in a Teflonlined autoclave. The content was heated to 80°C and kept with one week, and cooled to room temperature at a rate of 0.1 °C/min, giving colorless block crystals. Yield: ca. 38% based on H2BPDC. EA(%): C10H25NO14.5P2Zn2 (583.99): C, 20.56; H, 4.31; N, 2.40. Found: C, 20.63; H, 4.19; N, 2.31. IR (KBr pellets, cm-1): 3394 (m), 2974 (m), 2878 (w), 1594 (s), 1416 (m), 1092 (s), 996 (w), 948 (w), 778 (w), 675 (w).

2

C11H22NO12P2Zn2

C10H25NO14.5P2Zn2

552.97

583.99

Space group

P21/c

P21/c

Crystal system

Monoclinic

Monoclinic

a (Å)

6.4327(10)

6.4394(6)

b (Å)

30.2492(5)

28.798(3)

c (Å)

11.7675(2)

11.7113(11)

α (°)

90

90

β(°)

104.818(2)

104.643(8)

γ (°)

90

90

2213.62(7)

2101.2(4)

Z

4

4

F(000)

1124

1192

Dc (gcm-3)

1.659

1.846

μ (mm-1)

4.547

2.505

Rint

0.0612

0.0459

Collected reflections Unique reflections

81882

6935

4488

3704

GOF on F2

V

EXPERIMENTAL SECTION

mol-1)

1

(Å3)

0.980

0.964

,a

[I>2σ(I)]b

0.0689 0.1944

0.0546 0.1323

,a

data]b

0.0692 0.1946

0.0787 0.1436

R1 wR2

R1 wR2 [all

aR =∑||F |-|F ||/∑|F |.bwR ={∑[w(F 2 1 o c o 2 o

- Fc2)2]/∑w(Fo2)2}1/2

Crystallographic data collection and refinement. Data collection for the two compounds was performed by employing an XtaLAB-mini diffractometer (Mo-Kα radiation) at room temperature. The structures of 1 and 2 were solved and refined with the help of the SHELX-2016 software.[46] Some highly disordered guest water molecules which could not be determined in 1 and 2 have been treated with the “SQUEEZE” procedure.[47] Table 1 summarizes the detailed data for the structures of 1 and 2. Table S1-S2 lists some selected bond lengths and angles for the two compounds. CCDC number 1917761 and 1917762 correspond to 1 and 2.

RESULTS AND DISCUSSION Structures of {[(CH3)2NH2][Zn2(HEDP)(BPDC)0.5(H2O)2]·H2O} (1) and {[CH3NH3][Zn2(HEDP)(BPDC)0.5(H2O)2]·3.5H2O} (2). Both compounds 1 and 2 belong to monoclinic P21/c space group and show the isostructural architectures according to singlecrystal X-ray diffraction analysis. Herein, only the structure of 1 is discussed and depicted for clarity. In its asymmetric unit, there are a couple of Zn(II) ions, one HEDP molecule, a half of completely deprotonated BPDC ligand, a pair of coordinated water molecules, one dimethylamine counterion and one lattice water molecule. Though both Zn1 and Zn2 ions together with their surroundings adopt the octahedral [ZnO6]

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Figure 1. (a) The environment of Zn2+ center; (b) View of the dinuclear SBUs; (c) 2D layer network of 1; (d) 3D pillared-layer framework.

conjugated organic linkers are considered to be potential optical materials and versatile chemical sensors. Therefore, the solid-state luminescence properties of the two compounds, HEDP as well as the H2BPDC ligands were studied at ambient temperature. The free diphosphonate molecule exhibits a fluorescence emission band centered at 360 nm upon being excitated with UV light (λex = 320 nm, Figure S3). As displayed in Figure 2a and S4, the free H2BPDC ligand shows a blue emission centered at 400 nm with 340 nm radiation, which is probably assigned to the electron transition from π* to π or π* to n. For solids 1 and 2, upon excitated with 300 nm UV-light, the maximum emission peaks at 335 and 340 nm for 1 and 2 could be readily found, respectively. According to the previous studies, we can speculate that the emissions for the two compounds can neither be ascribed to ligand-to-metal charge transfer (LMCT) nor metal-to-ligand charge transfer (MLCT) in nature. This result indicates that the intra-ligand emissions are responsible for the photoluminescence of these compounds, corresponding to other Zn(II) compounds with Odonor building linkers.[48-51]

geometry, their coordination fashions are not same. As depicted in Figure 1a, Zn1 center connects with four phosphonate oxygen atoms from three symmetry-related HEDP moieties, one carboxylic oxygen atom from deprotonated BPDC molecule and one terminal coordinated water molecule. Differently, Zn2 ion is coordinated by three phosphonate-O and one hydroxyl-O atoms of two HEDP molecules, one carboxylic-O atom of BPDC and one water molecule. HEDP ligand in 1 adopts μ4-η2:η2:η1:η1:η1:η1:η0 tetradentate connection fashion to bridge/chelate four metal centers to generate a [Zn2(HEDP)3] building unit with Zn1···Zn2 distance of 3.09 Å (Figure 1b). The Zn-based dinuclear clusters is further extended through the -PO3 groups from HEDP to result in 2D Zn-HEDP layers, which contain the 4-memberd and 6-membered rings as depicted in Figure 1c. The inorganic-organic layers are packed in an -ABABfashion, and the remanent coordination sites of metal centers are completely filled by carboxyl group from BPDC pillars, leading to the 3D pillared-layer framework with the Zn···Zn distance between adjacent layers of 15.15 Å (Figure 1d). The 1D channel with a dimension of 11.38 × 15.15 Å2 could be observed along a-axis direction, which is occupied by dimethylamine cations formed from the in situ hydrolysis of DMF. From the viewpoint of topology, the HEDP molecule and [Zn2(HEDP)3] moiety can be treated as a three- and fourconnected node, respectively, and BPDC could be regarded as the linkers. Therefore the whole network could be viewed as a 2-nodal (3,4)-connected network (Figure S1). Luminescent Properties. Metal phosphonates fabricated from transition metal ions containing d10 configuration and

Detection of ions. By virtue of the good photoluminescence performance as well as the high water stability, solid 1 was chosen to investigate its sensing properties towards different exotic species. Firstly, to conduct the sensing experiments for metal ions, 5 mg as-synthesized samples of 1 were grounded and immersed in 5 mL aqueous solutions of M(NO3)x (1 mmol L-1; M = Li+, Na+, K+, Cu2+, Co2+, Cd2+, Ni2+ and Fe3+, respectively) for one hour to form the Mn+@1, and the photoluminescence emission spectra was then performed. It can be found that the luminescent intensity of 1 is dependent



Figure 2. (a) Solid-state emission spectra for H2BPDC, 1 and 2; (b) Luminescence intensity of 1 in aqueous solution containing various metal ions; (c) and (d) Emission spectra of aqueous solution 1 with various amounts of Cu2+ and Fe3+, respectively. Inset: the S-V plot for Cu2+ and Fe3+

different metal ions (Figure S5). Besides that, there is no obviously competitive adsorption between Cu2+/Fe3+ and the framework (Figure S7a). Thus the quenching effect can be a result of electron transfer process. Both Cu2+ and Fe3+ has unsaturated electronic state of the outer layers, which maybe act as excellent acceptors of excited electrons. When Cu2+ or Fe3+ are interacted with the framework of 1, electron transfer from organic ligands to metal ions may occur, which results in the decrease of luminescence intensity.

on the nature of metal ions, especially for Cu2+ and Fe3+, which exhibit the obvious turn-off luminescent quenching effect towards 1 (Figure 2b). To further explore the sensing sensitivity of 1 on Cu2+ and Fe3+, the concentration gradient experiment was carried out with Cu2+ and Fe3+ concentration ranging from 0 to 0.8 and 0.4 mM, respectively. As displayed in Figure 2c and 2d, the luminescence intensity gradually decreases with the increase of Fe3+/Cu2+ concentration. For Cu2+, as the concentration increased to 100 μM, about half of the emission intensity could be decreased. When the content of Cu2+ reaches to 800 μM, the luminescence quenching efficiency could be up to almost 80%. In addition, the samples 1 also exhibit the sensitive detection performance towards Fe3+. About 50% of the luminescence intensity has been reduced with Fe3+ concentration increasing to 100 μM. When the amount comes to 400 μM, the emission intensity could be declined for almost 80%. Moreover, the quenching efficiency (Ksv) could be quantitatively calculated using the Stern-Volmer equation: I0/I = 1 + Ksv[M], where I0 and I represent the emission intensities of the blank sample and Mn+@1, respectively, and [M] corresponds to the concentration.[52-53] The Ksv can be calculated from the slope values in the inset of Figure 4 to be 4.74×103 M-1 for Cu2+ and 7.31 ×103 M-1 for Fe3+, respectively, demonstrating its obvious luminescent quenching on these two metal ions. To investigate the quenching mechanism, PXRD patterns of compound 1 after sensing tests have been measured, which are in good agreement with the assynthesized 1, suggesting that the host skeleton remain unchanged after immersing in aqueous solution containing

Figure 3. Emission intensities of 1 with various anions.


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Figure 4. Emission spectra and Stern-Volmer plot for 1 with various amount of (a) IO4- and (b) Cr2O72− in water.

Figure 5. (a) Luminescent intensities of 1 in diverse solvents; (b) Emission spectra of aqueous solution 1 with various amounts of nitrobenzene solvent.

treatment with IO4- and Cr2O72− were identical with the simulated one, implying the structure did not collapse (Figure S6). The absorption spectrum of IO4-/Cr2O72− displays intense absorption bands in the ranges of 200-270 nm and 230310/310-400 nm (Figure S7b), showing a big overlap with the excitation band of 1, which is responsible for the quenching phenomenon.

Additionally, we have also investigated the detection performance of 1 towards various anions. 5 mg of sample 1 was dispersed in NaX aqueous solution (X = Br-, I-, SCN-, NO3-, ClO4-, BrO3-, IO4-, CO32-, S2O82- or Cr2O72-) to generate the suspension (1 × 10-3 M) and the luminescence spectra were then recorded with 300 nm excitation wavelength for all cases. As displayed in Figure 3, it is clearly found that most anions exert negligible or only minor influence on the luminescence intensity except for IO4- and Cr2O72− anions. The sensitization of the luminescence quenching of 1 towards these two anions was further studied. It was shown in Figure 4 that the luminescence intensities of 1 decreased rapidly upon increasing the concentration of IO4- ions. As the concentration finally reached to 400 μM, more than 70% of luminescence intensity could be quenched. When it comes to Cr2O72−, the luminescence of 1 was gradually weakened with increasing concentration of Cr2O72−, and could be completely quenched with a low concentration of 40 μM. The value of Ksv for IO4and Cr2O72- are 4.44×103 M-1 and 2.09×105 M-1, respectively. It is worth mentioning that the detect ability of 1 is much larger than those of previously reported MOF/CP sensors towards Cr2O72−, such as Eu3+@MIL-124 (Ksv = 6.034 × 104 M-1), [Zn(L5)(BBI)·(H2O)2] (Ksv = 1.168 × 104 M-1) and [Cd(IPA)(L6)]n (Ksv = 1.168 × 104 M-1).[54-56] The large Ksv suggests that compound 1 has the high sensitivity for the detection of trace Cr2O72−. The PXRD patterns of 1 after

Detection of solvent. Moreover, the sensing potential of 1 for different solvents was further explored. Various solvents including acetonitrile (CH3CN), N-methyl pyrrolidone (NMP), N,N-dimethylformamide (DMF), cyclohexane, N,Ndimethylacetamide (DMA), tetrahydrofuran (THF), methylbenzene, dimethyl sulfoxide (DMSO), trichloromethane (CH3Cl), nitrobenzene (NB) were used as the investigated reagents. The luminescence intensity of 1 is greatly dependent on the organic solvents, especially for NB, which appears as a significant species for luminescence quenching (Figure 5a). Furthermore, the luminescence intensities are measured by the addition of NB into the suspension of 1 (dispersing 5 mg of 1 sample into 5 mL of water) to investigate the quenching effect of NB. As shown in Figure 5b, with the NB concentration increasing from 0 to 0.6 ppm, the emission intensity of 1@aqueous solution decreases sharply with the emission color from bright blue to nearly black under UV light, which implies that compound 1 could be acted as an efficient luminescent sensor for NB. Decorated by an electron-withdrawing



(7) Gelfand, B. S.; Huynh, R. P. S.; Collins, S. P.; Woo, T. K.; Shimizu, G. K. H. Computational and Experimental Assessment of CO2 Uptake in Phosphonate Monoester Metal–Organic Frameworks. Chem. Mater. 2017, 29, 10469-10477. (8) Sheikh, J. A.; Jena, H. S.; Clearfield, A.; Konar, S. Phosphonate Based High Nuclearity Magnetic Cages. Acc. Chem. Res. 2016, 49, 1093-1103. (9) Goura, J.; Chandrasekhar, V. Molecular Metal Phosphonates. Chem. Rev. 2015, 115, 6854-6965. (10) Köhler, C.; Rentschler, E. Functionalized phosphonates as building units for multi-dimensional homo- and heterometallic 3d–4f inorganic–organic hybrid-materials. Dalton Trans. 2016, 45, 12854-12861. (11) Heering, C.; Francis, B.; Nateghi, B.; Makhloufi, G.; Lüdeke, S.; Janiak, C. Syntheses, structures and properties of group 12 element (Zn, Cd, Hg) coordination polymers with a mixedfunctional phosphonate-biphenyl-carboxylate linker. CrystEngComm 2016, 18, 5209-5223. (12) Bao, S.-S.; Zheng, L.-M. Magnetic materials based on 3d metal phosphonates. Coord. Chem. Rev. 2016, 319, 63-85. (13) Zhang, X.-L.; Cheng, K.; Wang, F.; Zhang, J. Chiral and achiral imidazole-linked tetrahedral zinc phosphonate frameworks with photoluminescent properties. Dalton Trans. 2014, 43, 285-289. (14) Paz, F. A. A.; Vilela, S. M. F.; Tomé, J. P. C. Layered Metal– Organic Frameworks Based on Octahedral Lanthanides and a Phosphonate Linker: Control of Crystal Size. Cryst. Growth Des. 2014, 14, 4873-4877. (15) Zheng, Y.-Z.; Pineda, E. M.; Helliwell, M.; Winpenny, R. E. P. MnII-GdIII Phosphonate Cages with a Large Magnetocaloric Effect. Chem. Eur. J. 2012, 18, 4161-4165. (16) Shimizu, G. K. H.; Vaidhyanathan, R.; Taylor, J. M. Phosphonate and sulfonate metal organic frameworks. Chem. Soc. Rev. 2009, 38, 1430-1449. (17) Zheng, T.; Yang, Z.; Gui, D.; Liu, Z.; Wang, X.; Dai, X.; Liu, S.; Zhang, L.; Gao, Y.; Chen, L.; Sheng, D.; Wang, Y.; Diwu, J.; Wang, J.; Zhou, R.; Chai, Z.; Albrecht-Schmitt, T. E.; Wang, S. Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system. Nat. Commun. 2017, 8, 15369. (18) Rhauderwiek, T.; Wolkersdörfer, K.; Øien-Ødegaard, S.; Lillerud, K.-P.; Wark, M.; Stock, N. Crystalline and permanently porous porphyrin-based metal tetraphosphonates. Chem. Commun. 2018, 54, 389-392. (19) Tian, H.; Su, J.-B.; Bao, S.-S.; Kurmoo, M.; Huang, X.-D.; Zhang, Y.-Q.; Zheng, L.-M. Reversible ON–OFF switching of single-molecule-magnetism associated with single-crystal-tosingle-crystal structural transformation of a decanuclear dysprosium phosphonate. Chem. Sci. 2018, 9, 6424-6433. (20) Gagnon, K. J.; Perry, H. P.; Clearfield, A. Conventional and Unconventional Metal–Organic Frameworks Based on Phosphonate Ligands: MOFs and UMOFs. Chem. Rev. 2012, 112, 1034-1054. (21) Yan, L.; Jiang, H.; Wang, Y.; Li, L.; Gu, X.; Dai, P.; Liu, D.; Tang, S.-F.; Zhao, G.; Zhao, X.; Thomas, K. M. One-step and scalable synthesis of Ni2P nanocrystals encapsulated in N,Pcodoped hierarchically porous carbon matrix using a bipyridine and phosphonate linked nickel metal–organic framework as highly efficient electrocatalysts for overall water splitting. Electrochim. Acta 2019, 297, 755-766. (22) Paul, A. K.; Kanagaraj, R.; Jana, A. K.; Maji, P. K. Novel amine templated three-dimensional zinc-organophosphonates with variable pore-openings. CrystEngComm 2017, 19, 6425-6435. (23) Zhang, J.-W.; Zhao, C.-C.; Zhao, Y.-P.; Xu, H.-Q.; Du, Z.-Y.; Jiang, H.-L. Metal–organic frameworks with improved moisture stability based on a phosphonate monoester: effect of auxiliary N-donor ligands on framework dimensionality. CrystEngComm 2014, 16, 6635-6644. (24) Dai, L.-L.; Zhu, Y.-Y.; Jiao, C.-Q.; Sun, Z.-G.; Shi, S.-P.; Zhou,

substituent -NO2 group, NB with a low LUMO energy is an excellent electron acceptor, which might drive the electrons from the ligand to guest species, resulting in the luminescence quenching phenomenon.

CONCLUSIONS A dual-ligand strategy was utilized to construct two isostructural Zn-phosphonates by introducing a linear carboxylate as coligand. The diphosphonate with a bridged/chelated coordination mode plays a significant role in the formation of 2D Zn-HEDP layers, which are further connected through the deprotonated BPDC pillars. Both the Zn-phosphonate products exhibit intense luminescent emission at room temperature. Notably, compound 1 shows remarkable luminescent sensing behavior towards different types of metal ion and solvent, revealing that it can be considered as multiple probes for target analytes [57-59].

ASSOCIATED CONTENT Supporting Information. Selected bond lengths and angles, PXRD and additional figures. CCDC number 1917761 and 1917762. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected]; [email protected]. Notes

The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS We are thankful to the support from National Natural Science Foundation of China (21571111, 21601099 and 21601101) and Beijing National Laboratory for Molecular Sciences (BNLMS).

REFERENCES (1) Xu, H.; Feng, L.; Huang, W.; Wang, Q.; Zhou, H. A water-stable Ni(ii) diphosphonate exhibiting water vapor adsorption and water-assisted high proton conductivity. New J. Chem. 2019, 43, 807-812. (2) Bao, S.-S.; Shimizu, G. K. H.; Zheng, L.-M. Proton conductive metal phosphonate frameworks. Coord. Chem. Rev. 2019, 378, 577-594. (3) Firmino, A. D. G.; Figueira, F.; Tomé, J. P. C.; Paz, F. A. A.; Rocha, J. Metal–Organic Frameworks assembled from tetraphosphonic ligands and lanthanides. Coord. Chem. Rev. 2018, 355, 133-149. (4) Armakola, E.; Colodrero, R. M. P.; Bazaga-García, M.; Salcedo, I. R.; Choquesillo-Lazarte, D.; Cabeza, A.; Kirillova, M. V.; Kirillov, A. M.; Demadis, K. D. Three-Component CopperPhosphonate-Auxiliary Ligand Systems: Proton Conductors and Efficient Catalysts in Mild Oxidative Functionalization of Cycloalkanes. Inorg. Chem. 2018, 57, 10656-10666. (5) Zhang, R.; Russo, P. A.; Feist, M.; Amsalem, P.; Koch, N.; Pinna, N. Synthesis of Nickel Phosphide Electrocatalysts from Hybrid Metal Phosphonates. ACS Appl. Mater. Interfaces 2017, 9, 14013-14022. (6) Shaffer, D. W.; Xie, Y.; Szalda, D. J.; Concepcion, J. J. Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts. J. Am. Chem. Soc. 2017, 139, 15347-15355.


Page 6 of 9

Page 7 of 9 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(25)

(26)

(27)

(28)

(29)

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

W.; Li, W.-Z.; Sun, T.; Luo, H.; Ma, M.-X. Syntheses, structures, luminescence and molecular recognition properties of four new cadmium carboxyphosphonates with 2D layered and 3D supramolecular structures. CrystEngComm 2014, 16, 5050-5061. Jones, S.; Vargas, J. M.; Pellizzeri, S.; O’Connor, C. J.; Zubieta, J. Solid state coordination chemistry: Structural consequences of varying diphosphonate tether length and fluoride incorporation in the copper–bisterpy/oxomolybdenum/organodiphosphonate system (bisterpy=2,2’:4’,4’’:2’’,2’’’-quarterpyridyl-6’,6’’-di-2pyridine). Inorg. Chim. Acta 2013, 395, 44-57. Fu, Z.; Zhang, J.; Zeng, Y.; Tan, Y.; Liao, S.; Chen, H.; Dai, J. Synthesis and structure of a mixed crystal containing tris(4pyridiniumyl)-1,3,5-triazine and benzenetetracarboxylate ions: constructing a new photochromic molecular system viaselfassembly. CrystEngComm 2012, 14, 786-788. Dong, D.-P.; Sun, Z.-G.; Tong, F.; Zhu, Y.-Y.; Chen, K.; Jiao, C.Q.; Wang, C.-L.; Li, C.; Wang, W.-N. Synthesis, structure, surface photovoltage and magnetic properties of a novel 3D homochiral manganese phosphonate with right-handed helical chains. CrystEngComm 2011, 13, 3317. Rocha, J.; Shi, F.-N.; Paz, F. A. A.; Mafra, L.; Sardo, M.; Cunha-Silva, L.; Chisholm, J.; Ribeiro-Claro, P.; Trindade, T. 3D–2D–0D Stepwise Deconstruction of a Water Framework Templated by a Nanoporous Organic–Inorganic Hybrid Host. Chem. Eur. J. 2010, 16, 7741-7749. Ma, Y.-J.; Han, S.-D.; Pan, J.; Mu, Y.; Li, J.-H.; Wang, G.-M. An inorganic–organic hybrid framework from the assembly of an electron-rich diphosphonate and electron-deficient tripyridyl moiety. J. Mater. Chem. C 2018, 6, 9341-9344. Liu, H.-H.; Ma, Y.-J.; Han, S.-D.; Li, J.-H.; Wang, G.-M. Zincdiphosphonates with extended dipyridine units: synthesis, structures, in situ reactions, and photochromism. Dalton Trans. 2019, 48, 3955-3961. Ge, B.-D.; Han, S.-D.; Wei, Q.; Li, J.-H.; Wang, G.-M. Coordination-driven strategy towards crystalline hybrid photochromic materials via the marriage of a non-photochromic extended dipyridine unit and zincophosphate. J. Mater. Chem. C 2019, 7, 3920-3923. Zhai, Z.-W.; Yang, S.-H.; Cao, M.; Li, L.-K.; Du, C.-X.; Zang, S.Q. Rational Design of Three Two-Fold Interpenetrated Metal– Organic Frameworks: Luminescent Zn/Cd-Metal–Organic Frameworks for Detection of 2,4,6-Trinitrophenol and Nitrofurazone in the Aqueous Phase. Cryst. Growth Des. 2018, 18, 7173-7182. Sun, P.; Zhang, S.; Xiang, Z.; Zhao, T.; Sun, D.; Zhang, G.; Chen, M.; Guo, K.; Xin, X. Photoluminescent sensing vesicle platform self-assembled by polyoxometalate and ionic-liquidtype imidazolium gemini surfactants for the detection of Cr3+ and MnO4− ions. J. Colloid Interface Sci. 2019, 547, 60-68. Li, N.; Yu, L.; Wang, J.; Gao, X.; Chen, Y.; Pan, W.; Tang, B. A mitochondria-targeted nanoradiosensitizer activating reactive oxygen species burst for enhanced radiation therapy. Chem. Sci. 2018, 9, 3159-3164. Yang, X. G.; Ma, L. F.; Yan, D. P., Facile synthesis of 1D organic–inorganic perovskite micro-belts with high water stability for sensing and photonic applications. Chem. Sci. 2019, 10, 4567-4572. Huang, J.; Li, Y.; Huang, R.-K.; He, C.-T.; Gong, L.; Hu, Q.; Wang, L.; Xu, Y.-T.; Tian, X.-Y.; Liu, S.-Y.; Ye, Z.-M.; Wang, F.; Zhou, D.-D.; Zhang, W.-X.; Zhang, J.-P. Electrochemical Exfoliation of Pillared-Layer Metal-Organic Framework to Boost the Oxygen Evolution Reaction. Angew. Chem. Int. Ed. 2018, 57, 4632-4636. Li, H.; Li, S. n.; Hou, X.; Jiang, Y.; Hu, M.; Zhai, Q.-G. Enhanced gas separation performance of an ultramicroporous pillared-layer framework induced by hanging bare Lewis basic pyridine groups. Dalton Trans. 2018, 47, 9310-9316. Hakimifar, A.; Morsali, A. High-sensitivity detection of

(39) (40)

(41)

(42)

(43)

(44)

(45)

(46) (47) (48)

(49)

(50)

(51)

(52)

(53)

(54)

(55)

nitroaromatic compounds (NACs) by the pillared-layer metalorganic framework synthesized via ultrasonic method. Ultrason. Sonochem. 2019, 52, 62-68. Gong, T.; Lou, X.; Gao, E.-Q.; Hu, B. Pillared-Layer Metal– Organic Frameworks for Improved Lithium-Ion Storage Performance. ACS Appl. Mater. Interfaces 2017, 9, 21839-21847. Hazra, A.; Jana, S.; Bonakala, S.; Balasubramanian, S.; Maji, T. K. Separation/purification of ethylene from an acetylene/ethylene mixture in a pillared-layer porous metal– organic framework. Chem. Commun. 2017, 53, 4907-4910. Otsubo, K.; Haraguchi, T.; Sakata, O.; Fujiwara, A.; Kitagawa, H. Step-by-Step Fabrication of a Highly Oriented Crystalline Three-Dimensional Pillared-Layer-Type Metal–Organic Framework Thin Film Confirmed by Synchrotron X-ray Diffraction. J. Am. Chem. Soc. 2012, 134, 9605-9608. Huo, Y.; Yang, L.; Niu, J.; Wang, J. Construction of organic– inorganic hybrid molybdophosphonate clusters with copper– bipyridine. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014, 131, 484-489. Niu, J.; Zhang, X.; Yang, D.; Zhao, J.; Ma, P.; Kortz, U.; Wang, J. Organodiphosphonate-Functionalized Lanthanopolyoxomolybdate Cages. Chem. Eur. J. 2012, 18, 6759-6762. Paul, A. K.; Kanagaraj, R.; Pant, N.; Naveen, K. Rare Examples of Amine-Templated Organophosphonate Open-Framework Compounds: Combined Role of Metal and Amine for Structure Building. Cryst. Growth Des. 2017, 17, 5620-5624. Shi, F.-N.; Almeida Paz, F. A.; Ribeiro-Claro, P.; Rocha, J. Transposition of chirality from diphosphonate metal–organic framework precursors onto porous lanthanide pyrophosphates. Chem. Commun. 2013, 49, 11668-11670. G. Sheldrick, Acta Crystallogr., Sect. C: Struct. Chem., 2015, 71, 3–8. A. L. Spek, J. Appl. Crystallogr., 2003, 36, 7–13. Tao, C.-L.; Chen, B.; Liu, X.-G.; Zhou, L.-J.; Zhu, X.-L.; Cao, J.; Gu, Z.-G.; Zhao, Z.; Shen, L.; Tang, B. Z. A highly luminescent entangled metal–organic framework based on pyridinesubstituted tetraphenylethene for efficient pesticide detection. Chem. Commun. 2017, 53, 9975-9978. Williams, D. E.; Martin, C. R.; Dolgopolova, E. A.; Swifton, A.; Godfrey, D. C.; Ejegbavwo, O. A.; Pellechia, P. J.; Smith, M. D.; Shustova, N. B. Flipping the Switch: Fast Photoisomerization in a Confined Environment. J. Am. Chem. Soc. 2018, 140, 76117622. Qi, Y.; Xu, H.; Li, X.; Tu, B.; Pang, Q.; Lin, X.; Ning, E.; Li, Q. Structure Transformation of a Luminescent Pillared-Layer Metal–Organic Framework Caused by Point Defects Accumulation. Chem. Mater. 2018, 30, 5478-5484. Foo, M. L.; Horike, S.; Duan, J.; Chen, W.; Kitagawa, S. Tuning the Dimensionality of Inorganic Connectivity in Barium Coordination Polymers via Biphenyl Carboxylic Acid Ligands. Cryst. Growth Des. 2013, 13, 2965-2972. Jing, T.; Chen, L.; Jiang, F.; Yang, Y.; Zhou, K.; Yu, M.; Cao, Z.; Li, S.; Hong, M. Fabrication of a Robust Lanthanide Metal– Organic Framework as a Multifunctional Material for Fe(III) Detection, CO2 Capture, and Utilization. Cryst. Growth Des. 2018, 18, 2956-2963. Yang, Y.; Qiu, F.; Xu, C.; Feng, Y.; Zhang, G.; Liu, W. A multifunctional Eu-CP as a recyclable luminescent probe for the highly sensitive detection of Fe3+/Fe2+, Cr2O72−, and nitroaromatic explosives. Dalton Trans. 2018, 47, 7480-7486. Xu, X.-Y.; Yan, B. Eu(III)-Functionalized MIL-124 as Fluorescent Probe for Highly Selectively Sensing Ions and Organic Small Molecules Especially for Fe(III) and Fe(II). ACS Appl. Mater. Interfaces 2015, 7, 721-729. Parmar, B.; Rachuri, Y.; Bisht, K. K.; Laiya, R.; Suresh, E. Mechanochemical and Conventional Synthesis of Zn(II)/Cd(II) Luminescent Coordination Polymers: Dual Sensing Probe for



Selective Detection of Chromate Anions and TNP in Aqueous Phase. Inorg. Chem. 2017, 56, 2627-2638. (56) Zhao, Y.; Xu, X.; Qiu, L.; Kang, X.; Wen, L.; Zhang, B. Metal– Organic Frameworks Constructed from a New ThiopheneFunctionalized Dicarboxylate: Luminescence Sensing and Pesticide Removal. ACS Appl. Mater. Interfaces 2017, 9, 1516415175. (57) Zhao, Y.; Wang, L.; Fan, N. N.; Han, M. L.; Yang, G. P.; Ma, L. F., Porous Zn(II)-Based Metal–Organic Frameworks Decorated with Carboxylate Groups Exhibiting High Gas Adsorption and Separation of Organic Dyes. Cryst. Growth Des.2018, 18, 7114-

7121. (58) Zheng, K.; Liu, Z.; Jiang, Y.; Guo, P.; Li, H.; Zeng, C.; Ng, S. W.; Zhong, S. Ultrahigh luminescence quantum yield lanthanide coordination polymer as a multifunctional sensor. Dalton Transactions 2018, 47, 17432-17440. (59) Fu, H.R.; Wang, N.; Qin, J. H.; Han, M. L.; Ma, L. F.; Wang, F., Spatial confinement of a cationic MOF: a SC-|SC approach for high capacity Cr(VI)-oxyanion capture in aqueous solution. Chem. Commun. 2018,54, 11645-11648.


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For Table of Contents Use Only

Multiple Detection Characteristics of Two Zinc-phosphonates: Syntheses, Crystal Structures and Luminescent Properties Author list: Hao-Hao Liu, Jie Pan, Zhen-Zhen Xue, Song-De Han, Jin-Hua Li and Guo-Ming Wang*

Synopsis: Two pillared-layer metal phosphonates have been successfully constructed exhibiting luminescent sensing of Cu2+/Fe3+, IO4-/Cr2O72- and nitrobenzene.

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Multiple Detection Characteristics of Two Zinc-phosphonates

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