A Series of Organic–Inorganic Hybrid Zinc Phosphites Containing

Feb 14, 2018 - Synopsis. We report another route for manufacturing the unprecedented example of three zeolite-related materials with extra-large-chann...
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A Series of Organic−Inorganic Hybrid Zinc Phosphites Containing Extra-Large Channels Chih-Min Wang,*,† Ming-Feng Pan,† Yong-Jie Lin,† Mei-Ying Chung,‡ Yuh-Sheng Wen,‡ Yung Chang,† Hsiu-Mei Lin,† and Todd Hsu† †

Institute of Bioscience and Biotechnology, National Taiwan Ocean University, Keelung, Taiwan 202, Republic of China Institute of Chemistry, Academia Sinica, Nankang, Taipei, Taiwan 115, Republic of China

‡

S Supporting Information *

ditions.30 Thus far, no example of an extra-large-channel framework with the combined structural features of both MOFs and zeolite-related compounds into a single compound has been reported. The bottom-up construction of new nanostructured frameworks and/or more open structures from simple building blocks is still one of the most difficult challenges in chemistry. Herein, we report a series of extra-large-channel zeolite-related materials whose structures are constructed from carboxylate organic linkers and inorganic zinc phosphite chains. The channel windows of zinc phosphites were translated from a square shape with dimensions of 19.9 Å × 19.9 Å (NTOU-1) to rhombus forms with dimensions of 23.3 Å × 12.3 Å (NTOU-2) and 31.5 Å × 12.8 Å (NTOU-3) by the replacement of either the organic templates or the organic ligands under synthesis conditions otherwise identical with those used for NTOU-1. The maximum pore volumes across the channel for (HOCA)Zn(BDC)0.5(HPO3) (NTOU-1), (H2DIA)Zn2(BDC)(HPO3)2 (NTOU-2), and (HOCA)2Zn2(BPDC)(HPO3)2 (NTOU-3) were 61.2%, 55.6%, and 58.0%, respectively (OCA = noctylamine; DIA = 1,12-diamnododecane; BDC = 1,4benzenedicarboxylate; BPDC = biphenyl-4,4′-dicarboxylate). The synthesis, structural diversity, photoluminescence (PL), and adsorption properties for dye molecules and lanthanide ions are also reported. Colorless needlelike crystals of NTOU-1 were obtained by heating a mixture of Zn(NO3)2·6H2O (0.5 mmol, 0.149 g), terephthalic acid (0.5 mmol, 0.083 g), OCA (2 mmol, 334 μL), HF(aq) (1 mmol, 36 μL, 48% solution), H3PO3 (1 mmol, 0.082 g), dimethylformamide (5 mL), and H2O (5 mL) under hydro(solvo)thermal reaction conditions at 150 °C for 2 days. NTOU-2 (NTOU-3) was synthesized under the reaction condition similar to that used for NTOU-1 except that OCA (terephthalic acid) was replaced with DIA (biphenyl-4,4′dicarboxylic acid). The powder X-ray diffraction (XRD) patterns of the three compounds are in good agreement with the patterns calculated on the basis of the structure determined by singlecrystal XRD (Figures S1−S3). The elemental analysis results were consistent with the chemical formulas. Anal. Found (calcd) for NTOU-1: C, 40.56 (40.30); H, 6.52 (6.48); N, 4.03 (3.92). Anal. Found (calcd) for NTOU-2: C, 36.67 (36.55); H, 5.75 (5.52); N, 4.37 (4.26). Anal. Found (calcd) for NTOU-3: C, 45.36 (45.53); H, 6.29 (6.37); N, 3.48 (3.54). The yields based

ABSTRACT: A series of organic−inorganic hybrid zinc phosphites with extra-large channels were synthesized and characterized by single-crystal X-ray diffraction. This is an unusual example of introducing 1,4-benzenedicarboxylate and/or biphenyl-4,4′-dicarboxylate ligands into the organically templated metal phosphite system to build extralarge-channel zeolite-related materials via hydro(solvo)thermal reactions. Those frameworks are composed of carboxylate linkers and inorganic tubes of zinc phosphites, translating their channel windows from a square shape (NTOU-1) to rhombus forms (NTOU-2 and NTOU-3) via the replacement of organic amines or ligands under synthesis conditions otherwise identical with those used to prepare NTOU-1. The synthesis, structural diversity, photoluminescence, and adsorption properties for dye molecules and lanthanide ions are also reported.

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ver the past several years, the design and synthesis of new nanostructured materials have been the subject of intensive research not only from a basic research perspective but also because of their potential applications in ion-exchange, molecular separation, catalysis, gas storage, and energy-related fields, which stem from their interesting structures with large channels (and/or pores).1−9 The families of zeolite-related materials (e.g., silicates, germanates, phosphates, and phosphites) and metal−organic frameworks (MOFs) are mainstream topics in the field of crystalline materials and dominate major research in the synthesis and characterization of new solid-state materials.1−33 Unlike the synthesis routes for controlling the porosities in MOF compounds through the selection of appropriate organic ligands as linkers, organic ammonium molecules used in the synthesis of zeolite-related compounds play a critical role as templates around which the inorganic polyhedral units assemble, resulting in the formation of inorganic frameworks with large windows. Landmark structures in the presence of organic amines have extended the upper limits of the inorganic channel sizes to 30-membered rings (MR) and 48MR in germanates,20−22 72MR in phosphites,23 24MR and 28MR in phosphates,24−27 and 18MR in silicates.28,29 To prepare new crystalline materials with nanostructured frameworks, 1,4benzenedicarboxylate and biphenyl-4,4′-dicarboxylate ligands, which are well-known organic building units used in MOF compounds, were introduced into a system of organically templated metal phosphite under hydro(solvo)thermal con© XXXX American Chemical Society

Received: December 22, 2017

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DOI: 10.1021/acs.inorgchem.7b03235 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry on zinc for NTOU-1, -2, and -3 were 67%, 78%, and 61%, respectively. Thermogravimetric analysis (TGA) of powder samples under O2 at a heating rate of 5 °C min−1 from 40 to 1000 °C showed two stages of overlapping weight-loss events (Figures S4−S6). The first step began at about 100, 230, and 210 °C for NTOU-1, -2, and -3, respectively. The powder XRD patterns for the final decomposition products of the title compounds after TGA confirmed the presence of Zn2P2O7. The observed overall weight loss of 57.34% for NTOU-1 (for NTOU-2, 54.25%; for NTOU-3, 60.30%) differs from the calculated value of 61.88% for the weight loss of 0.5·(C8H4O4), 0.5·(H2O), and 1·(C8H20N) [for NTOU-2, 58.50% for the loss of 1·(C8H4O4), 1·(H2O), and 1·(C12H30N2); for NTOU-3, 65.54% for the weight loss of 1· (C14H8O4), 1·(H2O), and 2·(C8H20N)]. The complex thermal behavior may be dominated by the dehydration of HPO3 groups, departure of organic amines and ligands, and oxidation of PIII to PV during the decomposition process for NTOU-1, 61.81% (57.34% + 4.47%) [for NTOU-2, 59.12% (54.25% + 4.87%); for NTOU-3, 64.34% (60.30% + 4.04%)]. The IR spectra (Figure S7) show the bands characteristic of the organic amines (∼3470 cm−1 for NTOU-1; ∼3464 cm−1 for NTOU-2; ∼3441 cm−1 for NTOU-3), carboxylate ligands (1617, 1679, and 1684 cm−1, respectively), and HPO3 units (P−H vibration bending; 1019, 1018, and 1008 cm−1, respectively). The gas-sorption studies (Figure S8) of NTOU-1 also show that the adsorption capacities for N2 (77 K), H2 (77 K), and CO2 (195 K) are 14.57 (1.79 for NTOU-2; 4.59 for NTOU-3), 4.47, and 6.98 cm3 g−1, respectively. A limited amount of gas uptake, elemental, and TG analyses indicates the presence of long-carbon-chain monoamines in the structure of NTOU-1. Suitable crystals of the title compounds were selected for single-crystal XRD analysis (Tables S1 and S2 include selected crystallographic information for the three compounds), from which the chemical formulas and structures were determined.34 The structure for NTOU-1 contains the following structural elements: one ZnO4 tetrahedron, one phosphite pseudotetrahedron, one octylamine molecule, and half of a terephthalate ligand (for NTOU-2, two ZnO4 tetrahedra, two phosphite pseudotetrahedra, one DIA group, and one terephthalate linker; for NTOU-3, two ZnO4 tetrahedra, two phosphite pseudotetrahedra, two octylamine molecules, and one BPDC ligand). The carboxylate ligands bridged Zn atoms in a bismonodentate coordination model with an unusual cis linkage for NTOU-3 and with the trans form for NTOU-1 and NTOU-2 (Figure 1a−c). Every P atom in these compounds is linked with three Zn atoms via O atoms and retains one H atom (P−H), whereas the Zn atom is coordinated by three phosphite O atoms and one carboxylate O atom. The different organic amines and/ or ligands used under similar conditions in the synthesis of NTOU-1 induce interesting structural diversities not only in the 1D inorganic zinc phosphite structures (Figure 1d−f) but also in their inorganic−organic hybrid frameworks with extra-large channels, which range from a square shape in NTOU-1 to rhombus forms in NTOU-2 and NTOU-3 (Figure 2). The ZnO4 and HPO3 tetrahedra connect together through corner-sharing O atoms to form inorganic zinc phosphite tubes with 6MR and 8MR for NTOU-1 and with 4MR and 8MR for NTOU-2 and NTOU-3, respectively (Figures 1d−f and 2). One openframework zinc phosphite consisting of inorganic chains and similar tubes of NTOU-1 was also reported.33 Herein, the title compounds represent a novel example of crystalline structures with the combined structural features of both MOFs and zeolite-related materials in a single compound,

Figure 1. Coordination environments and inorganic building units of 1D zinc phosphite tubes for NTOU-1 (a and d), NTOU-2 (b and e), and NTOU-3 (c and f). Yellow, green, red, gray, and blue circles respectively represent Zn, P, O, C, and H atoms. ZnO4 and HPO3 units are indicated in yellow (or large tetrahedra in gray) and green (or small tetrahedra in gray), respectively. Thermal ellipsoids are shown at 50% probability.

in which the individual metallophosphite tubes are interconnected through carboxylate linkers to form extra-large-channel frameworks. Their channel windows are shifted from square forms with dimensions of 19.9 Å × 19.9 Å in NTOU-1 to rhombus-shaped types with dimensions of 23.3 Å × 12.3 Å in NTOU-2 and 31.5 Å × 12.8 Å in NTOU-3 (Figure 2). The nonframework space within the structure was estimated to be 61.2% (through PLATON calculation) of the unit-cell volume for NTOU-1 (55.6% for NTOU-2 and 58.0% for NTOU-3). As reported in the literature, inorganic structure building units tend to link together to form dense structures, which makes the synthesis of new zeolite-related materials with large-channel openings difficult.20−29,33 Although Wang et al. recently reported a viable synthesis method for developing new crystalline solids that extended the largest channel size from 30MR and 48MR in germanates20−22 to 72MR in phosphites,23 examples of zeoliterelated crystals with large-channel-size frameworks remain limited.20−29,33 In this case, we propose another approach to synthesizing extra-large-channel structures by merging both mainstream topics (MOFs and zeolite-related solids) of crystalline materials into a single system whose unusual frameworks are structurally featured by aromatic carboxylate ligands and inorganic zinc phosphites. Interestingly, NTOU-1 showed selective adsorption by the negatively charged networks: the color of the powder sample changed from colorless to deep blue (Figure S9) when it (10.7 mg) was treated with 5 mL of a 0.6 mM methylene blue solution for 30 min (no significant difference in the sample color was observed after using an anionic dye, chrome yellow), indicating adsorption of the cationic dye by NTOU-1. The UV−vis spectra also showed that the concentration of the dye decreased with time and finally reached equilibrium in the presence of NTOU-1 (Figure S10). In addition, this compound exhibited variable luminescence color (under a hand-held lamp with 254 nm UV light) from blue to red (CIE, x = 0.65, y = 0.35), green (CIE, x = B

DOI: 10.1021/acs.inorgchem.7b03235 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

possesses higher N2 uptake capacity (35.34 cm3 g−1) than that of the as-synthesized sample (14.57 cm3 g−1), indicating that the adsorption of Eu cations into the structure of NTOU-1 improves the gas-adsorption performance. In summary, a series of organic−inorganic hybrid zinc phosphites with extra-large channels were synthesized under hydro(solvo)thermal conditions and subsequently characterized by single-crystal XRD. Their framework walls comprise aliphatic carboxylate ligands and inorganic zinc phosphite tubes, translating their channel window from a square shape (NTOU-1) into rhombus forms (NTOU-2 and NTOU-3) via the replacement of organic ligands or amine molecules under synthesis conditions otherwise identical with those used to prepare NTOU-1. The solid-state material (NTOU-1) also presents interesting properties such as PL and adsorption for dye molecules and lanthanide ions from aqueous solutions. Even though extensive attention has also been devoted to the synthesis of nanostructured compounds in MOF or zeolite-related fields because of their structural features and physicochemical properties, we are not aware of any other examples of the two aforementioned structural features being merged into a single compound with such extra-large-channel frameworks. Further research on the synthesis and applications of novel crystalline materials for functional applications is in progress.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b03235. Powder XRD patterns, TGA curves, IR, UV−vis, and luminescence spectra, gas-adsorption/desorption isotherms, elemental mapping images, crystallographic data, and selected bond lengths (PDF)

Figure 2. Inorganic−organic hybrid zinc phosphites with extra-largechannel windows shifted from a square shape in (a) NTOU-1 to rhombus forms in (b) NTOU-2 and (c) NTOU-3.

Accession Codes

0.303, y = 0.588), and yellow (CIE, x = 0.34, y = 0.58) emissions when the powder samples were stirred in aqueous ethanol solutions containing lanthanide cations (Figure S11).35 The emission spectra exhibited bands characteristic of lanthanide cations for Eu3+-adsorbed compounds (under 280 nm xenonlight excitation), 5D0 → 7F1 (593 nm), 5D0 → 7F2 (616 nm), and 5 D0 → 7F4 (697 nm) transitions; for Tb3+-adsorbed compounds (excited at 310 nm), 5D4 → 7F6 (488 nm), 5D4 → 7F5 (544 nm), and 5D4 → 7F4 (584 nm); for Eu3+/Tb3+-adsorbed compounds (under excitation at 290 nm), 5D4 → 7F6 (490 nm), 5D4 → 7F5 (545 nm), 5D0 → 7F2 (613 nm), and 5D0 → 7F4 (698 nm) (Figure S11).36−38 The powder XRD patterns of Tb3+- and Eu3+/ Tb3+-adsorbed products both contain one extra peak at 7.9° (Figure S12). Attempts to study the structural features for the Tb3+-adsorbed compound were unsuccessful. Single crystals after immersion in an aqueous ethanol solution of terbium chloride were no longer suitable for crystal structure analysis. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis confirmed red-, green-, and yellow-emitting compounds in the presence of Eu3+ (0.041 mg), Tb3+ (0.043 mg), and Eu3+/ Tb3+ (0.014 mg of Eu and 0.026 mg of Tb) cations per microgram, respectively. Elemental mapping measurements revealed the distribution of Eu and Tb cations within the Eu/ Tb-coadsorbed sample (Figure S13). The results from PL, ICPOES, and elemental mapping analyses indicate that the rare-earth ions are incorporated into the structure of NTOU-1. The gassorption study shows that the Eu3+-incorporated product

CCDC 1571473−1571475 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] or [email protected] (C.M.W.). ORCID

Chih-Min Wang: 0000-0002-0891-4523 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank the Ministry of Science and Technology of Taiwan for financial support (Grant MOST 105-2113-M-019-002-MY2).

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REFERENCES

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DOI: 10.1021/acs.inorgchem.7b03235 Inorg. Chem. XXXX, XXX, XXX−XXX