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Two New Zinc Phosphonates with Triazine-based Phosphonic Acids Rui-Biao Fu, Sheng-Min Hu, and Xin-Tao Wu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b00983 • Publication Date (Web): 16 Sep 2015 Downloaded from http://pubs.acs.org on September 17, 2015

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Table of Contents Two New Zinc Phosphonates with Triazine-based Phosphonic Acids Ruibiao Fu*, Shengmin Hu and Xintao Wu State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002 China *Corresponding author. E-mail: [email protected] Tel: +86-591-63173277

as-prepared o heating-treatment at 200 C

Intensity (arbitrary units)

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Crystal Growth & Design

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Wavelength (nm) A new 3D zinc phosphonate exhibits thermal stability and ion-exchange property, as well as displays near UV luminescence, which can be preserved after heating-treatment at 200 °C for 2 h under an air atmosphere.

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Two New Zinc Phosphonates with Triazine-based Phosphonic Acids Ruibiao Fu*, Shengmin Hu and Xintao Wu State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002 China *Corresponding author. E-mail: [email protected]. Tel: +86-591-63173277 ABSTRACT: Hydrothermal reactions of Zn(CH3COO)2·2H2O with two new triazine-based phosphonic acids 2,4,6-triglyphosate-1,3,5-triazine (H9L1) and 4,6-biglyphosate-2-hydroxyl-1,3,5-triazine (H6L2) afforded two new zinc phosphonates, namely, [(C5H14N2)Zn3(HL1)(H2O)]·3.5H2O (1) and [(C5H14N2)Zn2L2] ·3H2O (2). The two zinc phosphonates were structurally characterized through single-crystal X-ray diffraction. Compound 1 is a 3D framework in that Zn-O-P chains are connected by HL18- anions with hendecadentate modes. While in compound 2, each L26- anion links four Zn2 binuclear units to form a 3D framework. In both compounds 1 and 2, the protonated 2-methylpiperazine are encapsulated into the channels of 3D frameworks. TGA and powder XRD reveal that compounds 1 and 2 are thermally stable up to 200 and 160 °C under an air atmosphere, respectively. Compounds 1 and 2 display near UV and purple luminescence with maximum bands at 377 and 402 nm, respectively. It worth noting that the luminescence of solids 1 and 2 can be preserved after compounds 1 and 2 were heated at 200 and 160 °C for 2 h under an air atmosphere, respectively. In addition, ion-exchange property of compound 1 is also studied.

INTRODUCTION Metal phosphonates are of great research interest owing to their structural and compositional diversities, as well as their thermal and chemical stabilities for potential applications as porous materials, ion-exchangers, proton conductors, Langmuir-Blodgett Films, nonlinear optics, molecular sensors, catalysts, magnets and so on.1-13 Since the low solubility and crystallinity of metal phosphonates, it is still difficult to grow single crystals with suitable size and high quality for X-ray structural analysis. In recent three years, much effort has been devoted to modify phosphonic acids with additional groups, including amino, carboxylate, pyridyl, triazole, thienyl and imidazole.14-37 This is due to that additional groups can enrich coordination modes to improve the solubility and crystallinity of metal phosphonates. As a result, a variety of intriguing metal phosphonates have been obtained and structurally 2


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characterized, such as calcium phosphonates with tuned proton conductivity.19 On the other hand, triazine derivatives have been widely exploited to construct interesting coordination polymers, especially flexible polycarboxylate groups connecting with triazine rings.38-49 However, triazine rings with phosphonate groups have been rarely reported in previous work.50-51 Recently, an effect method has been performed to synthesize functionalized phosphonic acids by the combination of the N(CH2COOH)(CH2PO3H2) moiety and other organic groups. On the basis of these functionalized phosphonate ligands, many luminescent metal phosphonates with 3D frameworks, hybrid layers or polynuclear clusters, have been obtained under hydrothermal conditions.52-57 In this regard, we suggest that the combination of the N(CH2COOH)(CH2PO3H2) moiety and triazine rings would result in new functionalized phosphonate ligands. Thus, two new triazine-based phosphonic acids, Scheme 1), and 2,4,6-triglyphosate-1,3,5-triazine (H9L1, 4,6-biglyphosate-2-hydroxyl-1,3,5-triazine (H6L2, Scheme 1), have been successfully synthesized. Remarkably, the ligands H9L1 and H6L2 possess twenty-one and sixteen coordination sites, respectively. Such new multifunctional phosphonate ligands would adopt diversified coordination modes to form many interesting metal phosphonates. Herein, we report synthesis, crystal structures, thermal stabilities, luminescence, and ion-exchange property of two new three-dimensional (3D) zinc phosphonates: [(C5H14N2)Zn3(HL1)(H2O)]·3.5H2O (1) and [(C5H14N2)Zn2L2]·3H2O (2).

EXPERIMENTAL SECTION General. Phosphonate ligands H9L1 and H6L2 were prepared according to the reported method in previous literature.58-59 Other chemicals were obtained from commercial sources without further purification. Elemental (C, H, N) analyses were carried out with a Vario EL III element analyzer. While metals content were tested using a Ultrimas ICP spectrometer. Infrared spectra were obtained on a Nicolet Magna 750 FT-IR and a VERTEX 70 FT-IR spectrometers. The emission and excitation spectra were performed in solid state at room temperature with a F-7000 fluorescence spectrophotometer, while the lifetime and the quantum yield were investigated in solid state with an Edinburgh FLS920 fluorescence spectrometer. Thermogravimetric analysis (TGA) was performed on a Netzsch STA449C at a heating rate of 10 °C ·min-1 from room temperature to 1000 °C under an air gas flow. Powder X-ray diffraction (XRD) patterns were acquired on a DMAX-2500 and a Ultima IV diffractometers using Cu-Kα radiation under ambient environment. Synthesis of [(C5H14N2)Zn3(HL1)(H2O)]·3.5H2O (1). A mixture of Zn(CH3COO)2·2H2O (0.1021 g, 0.4651 mmol), H9L1 (0.0591 g, 0.102 mmol), and 2-methylpiperazine (1.00 g, 9.98 mmol) in 8.0 mL of distilled water with the pH value 3



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adjusted to around 3.9, was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 110 °C for 120 h. After being slowly cooled to room temperature, colorless crystals were obtained as a homogeneous phase based on powder XRD patterns. Yield: 0.0254 g (26 %). Anal. Calc. for C17H36N8O19.5P3Zn3: C 21.41, H 3.81, N 11.75 %. Found: C 21.86, H 3.85, N 11.33 %. IR (KBr pellet, cm-1): 3418m, 3030w, 2980w, 2959w, 2854w, 1716m, 1584m, 1563m, 1548s, 1538s, 1488s, 1403m, 1319m, 1254m, 1235m, 1197m, 1166m, 1075s, 1056m, 1002s, 972m, 854m, 808m, 768m, 550m. Synthesis of [(C5H14N2)Zn2L2]·3H2O (2). A mixture of Zn(CH3COO)2·2H2O (0.1235 g, 0.5626 mmol), H6L2 (0.0703 g, 0.163 mmol), and 2-methylpiperazine (0.2242 g, 2.238 mmol) in 6.0 mL of distilled water with the pH value adjusted to around 3.5, was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 120 °C for 40 h. After being slowly cooled to room temperature, pure orange crystals were manually separated from a small amount of unknown white powder. The pure orange crystals of 2 were obtained as a homogeneous phase based on powder XRD patterns. Yield: 0.0500 g (43 %). Anal. Calc. for C14H29N7O14P2Zn2: C 23.61, H 4.10, N 13.77 %. Found: C 23.09, H 4.20, N 13.27 %. IR (KBr pellet, cm-1): 3512m, 3458s, 3221w, 3140w, 3005w, 2961w, 1657m, 1630m, 1526s, 1387m, 1325w, 1290m, 1165m, 1123s, 976m, 854w, 806m, 729m, 669w, 554m. Heating Treatment: Solids 1-200, 1-250, and 2-160 were obtained after polycrystalline of 1, 1, and 2 were heated at 200, 250, and 160 °C for 2 h under an air atmosphere, respectively, and then naturally cooled to room temperature. Ion-exchange experiment. Synthesis of 1-Ag. Newly synthesized powder of 1 (0.0281g, 0.0295 mmol) was added to a solution containing AgNO3 (0.1690 g, 1.00 mmol) and 5.0 ml ethanol. Then, the mixture was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 80 °C for 20 h. After being cooled to room temperature, the final product was filtered, washed with 3 × 50 mL of distilled water and then 3 × 50 mL of ethanol, and dried under ambient temperature. ICP analysis shows that the content of Ag+ in solid 1-Ag is 0.151 mmol g-1. Elemental analyses: C 20.34, H 3.72, N 11.26 %. Synthesis of 1-Li. Newly synthesized powder of 1 (0.0304g, 0.0319 mmol) was added to a solution containing LiCl·H2O (0.0610 g, 1.01 mmol) and 6.0 ml ethanol. Then, the mixture was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 80 °C for 20 h. After being cooled to room temperature, the final product was filtered, washed with 2 × 50 mL of distilled water and then 2 × 50 mL of ethanol, and dried under ambient temperature. ICP analysis shows that the content of Li+ in solid 1-Li is 0.30 mmol g-1. Elemental analyses: C 21.08, H 3.48, N 11.57 %. Synthesis of 1-Eu. Newly synthesized powder of 1 (0.0314g, 0.0329 mmol) was added to a solution containing Eu(NO3)3·6H2O (0.4560 g, 1.022 mmol) and 6.0 ml ethanol. Then, the mixture was sealed into a Parr Teflon-lined autoclave (23 mL) and 4


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heated at 80 °C for 20 h. After being cooled to room temperature, the final product was filtered, washed with 2 × 50 mL of distilled water and then 2 × 50 mL of ethanol, and dried under ambient temperature. ICP analysis shows that the content of Eu3+ in solid 1-Eu is 0.037 mmol g-1. Elemental analyses: C 20.94, H 3.88, N 11.56 %. Synthesis of 1-Cu. Newly synthesized powder of 1 (0.0414g, 0.0434 mmol) was soaked in a solution containing CuCl2·2H2O (1.7004 g, 9.9771 mmol) and 5.0 ml of distilled water for 18 days. The color of the powder was turned from white into green. After filtration, the green powder was washed with a vast amount of distilled water until the filter liquor was colorless, and then dried under ambient temperature. ICP analysis shows that the content of Cu2+ in solid 1-Cu is 1.803 mmol g-1. Elemental analyses: C 17.72, H 3.76, N 9.94 %. X-Ray crystallography. X-ray data for compounds 1 and 2 were collected at 293(2) K on a Rigaku Mercury CCD/AFC diffractometer using graphite-monochromated Mo Kα radiation (λ(Mo-Kα) = 0.71073 Å). Data of compounds 1 and 2 were reduced with CrystalClear v1.3. Their structures were solved by direct methods and refined by full-matrix least-squares techniques on F2 using SHELXTL-97.60 All non-hydrogen atoms were treated anisotropically. Hydrogen atoms that bonded to carbon and nitrogen atoms, as well as hydrogen of carboxylate, were generated geometrically. While no attemps were performed to locate hydrogen atoms of water molecules and hydroxyl, as well as hydrogen atoms of protonated 2-methylpiperazine in 2. Crystallographic data for compounds 1 and 2 are summarized in Table 1. Selected bond lengths and angles for compounds 1 and 2 are listed in Tables 2 and 3, respectively. CCDC 1409896 (1) and 1409897 (2).

RESULSTS AND DISCUSSION Synthesis and Characterization. Compounds 1-2 were synthesized through the reaction of Zn(CH3COO)2·2H2O, 2-methylpiperazine, H9L1 and H6L2 under hydrothermal conditions. Powder XRD patterns of compounds 1-2 are in agreement with those of simulated single-crystal X-ray data, respectively. Furthermore, elemental analyses of compounds 1-2 also accord with respective calculated values. These results suggest that final products of compounds 1-2 are in homogeneous phase, respectively. Structural descriptions. Single-crystal X-ray diffraction reveals that the asymmetric unit of 1 contains three crystallographically independent Zn(II) ions, one HL18- anion, one protonated 2-methylpiperazine, one coordinated water molecule, as well as 3.5 free water molecules (Figure 1a). Zn1 is in a distorted [ZnO4] tetrahedral coordination geometry, which is defined by four phosphonate oxygen atoms from four different HL18- anions, respectively. Zn2 is surrounded by three HL18- anions into a 5



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distorted [ZnO4] tetrahedral coordination geometry. One HL18- anion chelates to Zn2 through two phosphonate oxygen atoms (O2, O11), resulting in a twelve-member ring (Zn-O-P-C-N-C-N-C-N-C-P-O). The other two HL18- anions are interacted with Zn2 through another two phosphonate oxygen atoms (O3b, O8a), respectively. Zn3 is surrounded by two HL18- anions and one coordinated water molecule (O16) into a distorted [ZnO4] tetrahedral coordination geometry. One HL18- anion chelates to Zn3 through one phosphonate oxygen atom (O7) and one carboxylate oxygen atom (O9), resulting in an eight-member ring (Zn-O-P-C-N-C-C-O), while the other HL18- anion is interacted with Zn3 through another one carboxylate oxygen atom (O4d). The bond lengths of Zn-O are in the range of 1.862(8)-1.992(8) Å, which are comparable with other reported zinc phosphonates. 52-56,61-62 On the other hand, the HL18- anion exhibits a hendecadentate mode to combine nine Zn(II) ions through nine phosphonate and two carboxylate oxygen atoms (Figure 1b). To the best of our knowledge, the coordination number of HL18- anion is larger than those of triazine-based carboxylate ligands.38-49 The protonated carboxylate atom (O14) provides one hydrogen atom to form a strong hydrogen bonding with another carboxylate atom (O14···O10e, 2.547(11) Å). While the protonated 2-methylpiperazine provides three hydrogen atoms to form three hydrogen bondings with phosphonate oxygen atoms (N7···O7f, 2.809(16) Å; N8···O3, 2.989(17) Å; N8···O12, 2.930(19) Å). Meanwhile, the protonated 2-methylpiperazine also hydrogen bonds with one free water molecule (N7···O20, 2.87(6) Å). As shown in Figure 1c, [Zn1O4] and [Zn2O4] tetrahedra are bridged by [P1CO3] and [P2CO3] tetrahedra through corner-sharings. And [Zn3O4] tetrahedra are interacted with [Zn1O4] and [Zn2O4] tetrahedra via [P3CO3] tetrahedra through corner-sharings. As a result, a wave-like Zn-O-P chain along a axis is formed. The Zn-O-P chains are further cross-linked by HL18- anions into a 3D framework (Figure 1d-e). The 3D framework contains two type channels along a and c axis, respectively. The protonated 2-methylpiperazine are encapsulated into the channels through the above-mentioned hydrogen bondings between the protonated nitrogen atoms and phosphonate oxygen atoms. The asymmetric unit of 2 consists of one Zn(II) ion and half L26- anion, half protonated 2-methylpiperazine, as well as 1.5 free water molecules (Figure 2a). Zn1 is surrounded by three L26- anions into a distorted [O3ZnN] tetrahedral coordination geometry. One L26- anion chelates to Zn1 through one phosphonate oxygen atom (O1) and a nitrogen donor (N2) of the triazine ring, resulting in a seven-member ring (Zn-O-P-C-N-C-N), while the other two L26- anions contact Zn1 via one phosphonate oxygen atom (O2a) and one carboxylate oxygen atom (O4b), respectively. The bond lengths of Zn-O are in the range of 1.942(4)-1.971(4) Å, which are comparable with other reported zinc phosphonates.52-56,61-62 The bond length of Zn1-N2 is 2.022(4) Å. 6


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On the other hand, each L26- anion exhibits an octadentate mode to combine six Zn(II) ions through four phosphonate and two carboxylate oxygen atoms, as well as two nitrogen donors of the triazine ring. This is obviously different from those in compound 1, in that the nitrogen donors of triazine ring do not take part in coordination. As shown in Figure 2b, two neighboring Zn(II) ions are bridged by two O-P-O groups to form a binuclear unit. Each L26- anion connects four neighboring binuclear units. Thus, such binuclear units are cross-linked by L26- anions into a 3D framework (Figure 2c). Thermal Stabilities. TGA and powder XRD measurements were carried out to examine thermal stabilities (Figure 3). For solid 1, an obvious stage occurs from room temperature to 150 °C with a 10.5% weight loss, which is attributed to the loss of 4.5 water molecules per formula (calculated 9.1%). Upon further heating, little weight losses appear until an abrupt stage starts from 290 °C due to the decomposition of the HL18- anion and the protonated 2-methylpiperazine. As a result, the 3D framework collapses. A TGA curve of solid 2 indicates that there is an obvious stage in the temperature range of 40-160 °C with 7.87% observed weight loss, which corresponds with the release of three free water molecules per formula (calculated 7.58%). Then, the subsequent weight loss over 300 °C is assigned to the decomposition of L26- anion and the protonated 2-methylpiperazine, resulting in the collapse of the 3D framework. Furthermore, powder XRD patterns of solids 1-200 and 2-160 are essentially in agreement with those of as-prepared 1 and 2, respectively. These results indicate that the 3D frameworks of compounds 1 and 2 are stable up to 200 and 160 °C under an air atmosphere, respectively. Luminescent Properties. Solid-state luminescent properties were investigated under ambient temperature. Solid 1 displays near ultraviolet (UV) luminescence with a maximum band at 377 nm (Figure 4). The external quantum yield reaches 2.9% upon excitation at 293 nm. Since both emission and excitation profiles of solid 1 are similar to those of H9L1, the UV emission of solid 1 may be assigned to ligand-centered π-π* transition.39 The emission peak of solid 1 shows a 17 nm bathochromic shift in comparison with that of H9L1. Solid 1-200 can also displays similar UV emission with a maximum band at 363 nm. This result accords with the observation that the 3D framework of solid 1 is stable up to 200 °C under an air atmosphere. Although the structure of solid 1-250 disagrees with that of as-prepared 1, solid 1-250 can also emit similar near UV luminescence. This indicates that the near UV luminescence can be preserved after compound 1 was heated at 250 °C for 2 h under an air atmosphere. In addition, solid 1 can display more strong near UV luminescence with a maximum band at 367 nm at 10 K. Solid 2 displays purple luminescence with a maximum band at 402 nm under excited at 273 nm (Figure 5). The external quantum yield reaches 9.05% upon 7



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excitation at 273 nm. The lifetime for λem = 402 nm is 1.82(4) ns. Since both emission and excitation profiles of solid 2 are in agreement with those of H6L2, the purple emission of solid 2 may be assigned to ligand-centered π-π* transition.39 The emission peak of solid 2 shows a 41 nm bathochromic shift in comparison with that of H6L2. Furthermore, the purple emission of solid 2 can be preserved after compound 2 was heated at 160 °C for 2 h under an air atmosphere. This result accords with the observation that the 3D framework of solid 2 is stable up to 160 °C under an air atmosphere. Ion-exchange. The theoretical ion exchange capacity of solid 1 is 2.097 meq g-1. ICP measurements reveals that the contents of Ag+, Li+, and Eu3+ in solids 1-Ag, 1-Li, and 1-Eu are 0.151, 0.30, and 0.037 mmol g-1, respectively. Correspondingly, the C content of solids 1-Ag, 1-Li, and 1-Eu is less than that of as-prepared 1. These results indicate that partial protonated 2-methylpiperazine in solid 1 can be exchanged by Ag+, Li+, and Eu3+ cations, which reach 7.2, 14, and 5.3% of the total ion exchange capacity, respectively. Powder XRD patterns of solids 1-Ag, 1-Li, and 1-Eu are in agreement with those of as-prepared 1, indicating that the framework of solid 1 remains its original framework after ion-exchanging with Ag+, Li+ and Eu3+ cations. Similar to solid 1, solids 1-Ag, 1-Li, and 1-Eu can also displays near UV luminescence with maximum bands around 377 nm. It worth noting that luminescent intensity of solid 1-Ag can be irreversibly weakened by UV irradiation (Figure 6). For instance, after irradiation with UV radiation at 290 nm for 5 minutes, luminescent intensity of solid 1-Ag can be weakened to 30%. Meanwhile, the color of solid 1-Ag changed from white to black. It is well known that excessive exposure to UV radiation would cause skin cancer, cataracts, and other eye diseases. Particularly, the eyes are most sensitive to UV radiation with the wavelength around 280 nm. Since UV radiation is invisible to stimulate the natural defenses of the eyes, facile synthesis and thermal stability make solid 1-Ag an attractive material to be used for the sensing of UV radiation. By contrast to the low metal contents in solids 1-Ag, 1-Li, and 1-Eu, the content of Cu2+ in solid 1-Cu reaches up to 1.803 mmol g-1. Powder XRD patterns of solid 1-Cu also accords with those of as-prepared 1, indicating that the framework of solid 1 remains its original framework after ion-exchanging with Cu2+ cation. And no emission of 1-Cu can be detected under our experiment.

CONCLUSION Based on new functionalized phosphonate ligands, two 3D zinc phosphonates, namely, [(C5H14N2)Zn3(HL1)(H2O)]·3.5H2O (1) and [(C5H14N2)Zn2L2]·3H2O (2), have been successfully synthesized and structurally characterized. Both compounds 8


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1-2 are interesting 3D frameworks containing protonated 2-methylpiperazine. TGA and powder XRD reveal that 3D frameworks of compounds 1 and 2 are thermally stable up to 200 and 160 °C under an air atmosphere, respectively. Solids 1 and 2 display near UV and purple luminescence, respectively. It worth noting that the luminescence of solids 1 and 2 can be preserved after compounds 1 and 2 were heated at 200 and 160 °C for 2 h under an air atmosphere, respectively. Furthermore, solid 1 exhibits ion-exchange property maintaining the integrity of the framework. In future, we will try to synthesize other functionalized phosphonic acids by the combination of triazine ring with the N(CH2COOH)(CH2PO3H2) moiety, along with amino acids, such as proline and alanine. Then, such functionalized phosphonate ligands will be exploited to prepare new metal phosphonates with interesting structures and investigate their properties. .

ASSOCIATED CONTENT Supporting Information Crystallographic data in CIF format (CCDC 1409896 (1) and 1409897 (2)), IR spectra, PXRD patterns and luminescent plots. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *Email: [email protected] (R. B. Fu) Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This research was supported by grants from the National Science Foundation of China (21173220 and 21373219) and the National Basic Research Program of China (973 Program, 2014CB845603).

REFERENCES (1) Gagnon, K. J.; Perry, H. P.; Clearfield, A. Chem. Rev. 2012, 112, 1034-1054. (2) Clearfield, A.; Demadis, K. Metal Phosphonate Chemistry From Synthesis to Applications, The Royal Society of Chemistry, 2012. (3) Boldog, I.; Domasevitch, K. V.; Baburin, I. A.; Ott, H.; Gil-Hernández, B.; Sanchiz, J.; Janiak, C. CrystEngComm. 2013, 15, 1235-1243. 9



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Commun. 2014, 50, 14831-14834. (52) Fu, R. B.; Hu, S. M.; Wu, X. T. CrystEngComm. 2012, 14, 3478-3483. (53) Fu, R. B.; Hu, S. M.; Wu, X. T. CrystEngComm. 2012, 14, 5761-5764. (54) Fu, R. B.; Hu, S. M.; Wu, X. T. CrystEngComm. 2013, 15, 8937-8940. (55) Fu, R. B.; Hu, S. M.; Wu, X. T. CrystEngComm. 2014, 16, 5387-5393. (56) Fu, R. B.; Hu, S. M.; Wu, X. T. Cryst. Growth Des. 2015, 15, 3004-3014. (57) Fu, R. B.; Hu, S. M.; Wu, X. T. CrystEngComm. 2013, 15, 802-807. (58) de Hoog, P.; Gamez, P.; Driessen, W. L.; Reedijk, J. Tetrahedron Lett. 2002, 43, 6783-6786. (59) Zhu, Q. L.; Sheng, T. L.; Fu, R. B.; Hu, S. M.; Chen, J. S.; Xiang, S. C.; Shen, C. Wu, X. T. Cryst. Growth Des. 2009, 9, 5128-5134. (60) Sheldrick, G. M. SHELXT 97, Program for Crystal Structure Refinement, University of Göttingen, Germany, 1997. (61) Fu, R. B.; Hu, S. M.; Wu, X. T. CrystEngComm. 2011, 13, 2331-2335. (62) Fu, R. B.; Hu, S. M.; Wu, X. T. CrystEngComm. 2011, 13, 6334-6336.

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Page 13 of 27

For Table of Contents Use Only

Two New Zinc Phosphonates with Triazine-based Phosphonic Acids Ruibiao Fu*, Shengmin Hu and Xintao Wu State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002 China *Corresponding author. E-mail: [email protected] Tel: +86-591-63173277

a s -p r e p a r e d h e a tin g -tr e a tm e n t a t 2 0 0

o

C


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


3 0 0

3 5 0

4 0 0

W

a v e le n g th

4 5 0

5 0 0

(n m )

A new 3D zinc phosphonate exhibits thermal stability and ion-exchange property, as well as displays near UV luminescence, which can be preserved after heating-treatment at 200 °C for 2 h under an air atmosphere.

13



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Table 1. Crystal Data and Refinement Details for Compounds 1-2. Compounds Formula FW Space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z T(K) Measured/unique/observed reflections Dcalcd (g cm3) µ (mm-1) GOF on F2 Rint R1a [I>2σ(I)] wR2b [all data] a

1 C17H36N8O19.5P3Zn3 953.56 P-1 10.137(6) 11.802(7) 13.768(8) 86.899(12) 89.523(9) 88.343(11) 1644.0(17) 2 293(2) 12788/7027/5003

2 C14H29N7O14P2Zn2 712.12 Pnma 15.444(8) 17.895(10) 8.979(5) 90 90 90 2482(2) 4 293(2) 17881/2925/2563

1.785 2.399 1.091 0.0501 0.0829 0.2276

1.906 2.146 1.195 0.0487 0.0617 0.1594

R1 = ∑(||Fo| - |Fc||) / ∑ |Fo|. b wR2 = {∑w [(F2o − F2c)] / ∑w [(F 2o ) 2]}0.5

Table 2. Selected Bond Lengths (Å) and Angles (deg) for 1. Zn(1)-O(1) Zn(1)-O(6)a Zn(1)-O(12)c Zn(1)-O(13)b Zn(2)-O(2) Zn(2)-O(3)b

1.954(6) 1.944(6) 1.951(6) 1.948(6) 1.862(8) 1.992(8)

Zn(2)-O(8)a Zn(2)-O(11) Zn(3)-O(4)d Zn(3)-O(7) Zn(3)-O(9) Zn(3)-O(16)

1.967(7) 1.918(6) 1.992(8) 1.868(7) 1.919(7) 1.983(12)

O(1)-Zn(1)-O(6)a 115.6(3) O(3)b-Zn(2)-O(8)a 97.2(3) O(1)-Zn(1)-O(12)c 115.5(3) O(3)b-Zn(2)-O(11) 98.7(3) b c O(1)-Zn(1)-O(13) 109.7(3) O(8) -Zn(2)-O(11) 114.5(3) a c d O(6) -Zn(1)-O(12) 98.4(3) O(4) -Zn(3)-O(7) 115.2(3) O(6)a-Zn(1)-O(13)b 112.4(3) O(4)d-Zn(3)-O(9) 96.2(3) c b d O(12) -Zn(1)-O(13) 104.3(3) O(4) -Zn(3)-O(16) 105.5(5) b O(2)-Zn(2)-O(3) 131.2(4) O(7)-Zn(3)-O(9) 117.7(3) O(2)-Zn(2)-O(8)a 101.3(4) O(7)-Zn(3)-O(16) 119.2(6) O(2)-Zn(2)-O(11) 113.4(3) O(9)-Zn(3)-O(16) 99.5(6) Symmetry codes: a - x + 1, - y + 1, - z; b - x + 1, - y + 1 , - z + 1; c x - 1, y, z; d - x + 1, - y, - z.

14


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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


Table 3. Selected Bond Lengths (Å) and Angles (deg) for 2. Zn(1)-N(2) Zn(1)-O(1)

2.022(4) 1.971(4)

Zn(1)-O(2)a Zn(1)-O(4)b

N(2)-Zn(1)-O(1) 104.82(18) O(1)-Zn(1)-O(2)a a 102.75(18) O(1)-Zn(1)-O(4)b N(2)-Zn(1)-O(2) N(2)-Zn(1)-O(4)b 132.29(18) O(2)a-Zn(1)-O(4)b Symmetry codes: a - x, - y + 1, - z; b x + 1/2, y, - z + 1/2.

1.942(4) 1.961(4) 110.47(18) 105.57(17) 99.95(19)

Scheme 1 Structures of H9L1 (left) and H6L2 (right).

15



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Page 16 of 27

(a) (b)

(c)

c a (d)

c b

(e)

a b

Figure 1. Ball-stick view of (a) the coordination environment of Zn(II) ions, (b) the coordination mode of HL18- anion, as well as (c) Zn-O-P chain, (d,e) polyhedral view of the 3D framework in 1. [ZnO4]: green tetrahedron; [PCO3]: yellow tetrahedron. Blue-green lines represent hydrogen bonding. Unrelated atoms are omitted for clarity. Symmetry codes: a - x + 1, - y + 1, - z; b - x + 1, - y + 1, - z + 1; c x - 1, y, z ; d - x + 1, - y, - z; e x + 1, y, z; f x - 1, y, z + 1

16


Page 17 of 27

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


(a)

(b)

b

(c)

a

Figure 2. (a) Ball-stick view of the coordination environment of Zn(II) ion and the coordination mode of L26- anion, (b) four Zn2 binuclear units around the L26- anion, (c) polyhedral view of the 3D framework in 2. [ZnNO3]: green tetrahedron; [PCO3]: yellow tetrahedron. Unrelated atoms are omitted for clarity. Symmetry codes: a - x, y + 1, - z; b x + 1/2, y, - z + 1/2. 17



Weight loss (%)

100

1 2

80

60

40 200

400 600 o Temperature ( C)

800

1000

Figure 3. TGA curves of solids 1-2.

1 1-200


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

Page 18 of 27

300

350

400

450

500

Wavelength (nm) Figure 4. Luminescent emission spectra of solids 1 and 1-200

18


Page 19 of 27

2 2-160

Intensity (arbitrary units) 300

350

400

450

500

Wavelength (nm) Figure 5. Luminescent emission spectra of solids 2 and 2-160.

0 min 5 min


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


250

300

350

400

450

500

Wavelength (nm) Figure 6. Luminescent emission spectra for solid 1-Ag with different UV irradiation times at 290 nm.

19



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Supporting information Two New Zinc Phosphonates with Triazine-based Phosphonic Acids Ruibiao Fu*, Shengmin Hu, Xintao Wu State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002 China Corresponding author. E-mail: [email protected]

1 2

4000

3000

2000 -1 Wavenumbers (cm )

1000

Figure S1. IR spectra of solids 1 and 2.

20


(c)

(b)

(a) 10

20

30o

40

50

2θ / Figure S2. Powder XRD patterns of 1 (a) simulated from single-crystal X-ray data,

and experimental data for solids 1 (b) and 1-200 (c).

Relative Intensity

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


Relative Intensity

Page 21 of 27

(c)

(b)

(a) 10

20

30

2θ /

o

40

50

Figure S3. Powder XRD patterns of 2 (a) simulated from single-crystal X-ray data, and experimental data for solids 2 (b) and 2-160 (c).

21


Excitation (λem=370nm)

200

Page 22 of 27

Emission (λex=270nm)

300

400

500

Wavelength (nm) Figure S4. Luminescent emission and excitation spectra of solid 1


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




200


300

400

500

Wavelength (nm) Figure S5. Luminescent emission and excitation spectra of solid 1-200.

22



200


300

400

500



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



Page 23 of 27


200

250


300

350

400

450

500

Wavelength (nm)

Figure S7. Luminescent emission and excitation spectra of H9L1.

23



200

250

Page 24 of 27


300

350

400

450

500

Wavelength (nm) Figure S8. Luminescent emission and excitation spectra of solid 2.


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





200

250

300

350

400

450

500


24


Page 25 of 27



200


250

300

350

400

450

500

Wavelength (nm) Figure S10. Luminescent emission and excitation spectra of H6L2.


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


0

2

4

6

8

10

12

Time (ns) Figure S11. Luminescent intensity as a function of time for compound 2 at room temperature (λem = 402 nm).

25


1-Ag

1-Li 1-Eu as-prepared 1 10

20

2θ /

o

30

40

Figure S12. PXRD patterns of as-prepared 1, 1-Ag, 1-Li and 1-Eu.

1-Li 1-Eu


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

Page 26 of 27

Relative Intensity


300

350

400

450

500

550

Wavelength (nm) Figure S13. Luminescent emission spectra for solids 1-Li and 1-Eu.

26


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


Relative Intensity

Page 27 of 27

1-Cu

as-prepared 1 10

20

2θ /

o

30

40

Figure S14. PXRD patterns of as-prepared 1 and 1-Cu.Inset: photograph of 1-Cu.

27


Two New Zinc Phosphonates with Triazine-Based Phosphonic ... - NSFC

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