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Synthesis and characterization of a new open-framework mixed-valence aluminum–iron phosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)]
Inorganic Chemistry Communications 47 (2014) 99–101
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Synthesis and characterization of a new open-framework mixed-valence aluminum–iron phosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)] Yanan Guo a,b, Yuchen Qiu a, Jiyang Li a, Lang Shao a, Xiaowei Song a,⁎ a
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China Laboratory of Environmental Science and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011, China
b
a r t i c l e
i n f o
Article history: Received 10 June 2014 Received in revised form 18 July 2014 Accepted 21 July 2014 Available online 22 July 2014 Keywords: Open framework Aluminophosphate Iron Mixed-valence
a b s t r a c t A new open-framework aluminum–iron phosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)] (denoted as FeAPO-CJ51), with mixed-valence iron (II, III) has been hydrothermally synthesized by using piperazine as the template. The three-dimensional framework of FeAPO-CJ51 is constructed by the connection of metal-centered MOn (M = Fe/Al, n = 4, 5, 6) polyhedra and PO4 tetrahedra, which contains interconnecting 8-ring channels along the [010] and [001] directions. Diprotonated piperazine cations locate in the 8-ring channels to compensate the negative charge of the anionic framework. Mössbauer and magnetic susceptibility measurements show that equal amounts of Fe2+ and Fe3+ are present in FeAPO-CJ51, which undergo the long-range antiferromagnetic interactions. © 2014 Published by Elsevier B.V.
Inorganic open-framework materials are an important class of functional materials owing to their widespread applications as ion exchangers, battery materials, catalysts, nonlinear optics, and gas storage/adsorption materials [1–3]. A large number of open-framework compounds with rich structure and charming properties have been synthesized under hydrothermal or solvothermal conditions [4,5]. The mixed aluminum–iron phosphate open-framework compounds have received considerable interest due to their rich structural diversity [6,7] and other promising properties including magnetic properties [8] and activities in some specific catalytic reactions [9]. For example, Fesubstituted AlPO4-5 calcined at relatively high temperature (823 K) was applied in the selective oxidation of benzene, and showed high selectivity to phenol [10]. Some of the dense ferrophosphates have been used for the selective oxidative dehydrogenation of isobutyric acid into methacrylic acid [11,12]. The mixed aluminum–iron phosphate cacoxenite [13] represents the most remarkable example of this family. Its open framework contains extra large channels of 14.2 Å, in which water molecules are trapped. In aluminum–iron phosphate structures, the oxidation state of Fe atoms are observed as + 3, + 2 or mixed valences, but these Fe atoms are often in the same coordination environments. The reports of metal aluminophosphates contain mixedvalence irons with different coordination states which are limited [14]. In this paper, we present a new 3-D aluminum–iron phosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)](denoted as FeAPO-CJ51) templated by piperazine, which contains interconnecting 8-ring channels along ⁎ Corresponding author. E-mail address: [email protected] (X. Song).
http://dx.doi.org/10.1016/j.inoche.2014.07.026 1387-7003/© 2014 Published by Elsevier B.V.
the [010] and [001] directions, and mixed-valence Fe(II)/Fe(III) atoms. The syntheses, structure, and magnetic properties have been studied. FeAPO-CJ51 was hydrothermally synthesized in the presence of piperazine as the template [15], which was characterized by singlecrystal X-ray diffraction structural analysis [16] and other characterization techniques. Crystallographic data, selected bond lengths and angles for FeAPO-CJ51 are summarized in Tables S1 and S2, respectively. FeAPO-CJ51 crystallizes in the triclinic space group P-1 (No. 2). Its cell dimensions are: a = 9.057(2) Å, b = 12.606(3) Å, c = 14.623(4) Å, α = 89.547(4)°, β = 86.530(4)° and γ = 72.512(4)°. Fig. 1 shows the thermal ellipsoids of FeAPO-CJ51. The crystallographically independent Fe atom occupying Fe(1) site is 4-coordinated and the crystallographically independent Al atom occupying Al(4) and Al(7) sites are 5-coordinated. While other metal sites (M(2), M(5), M(3) and M(6)) are co-occupied by Fe and Al atoms, which present four, five, and six coordinations, with the occupancies of Fe atom of 60%, 15%, 10%, and 15% respectively. The occupancy of Fe atom in each metal site was determined by the refinements using the SHELXTL 97, which is consistent with the bond lengths of Fe/Al\O. Strict alternation of MOn (M = Fe/Al, n = 4, 5, 6) polyhedra and PO4 tetrahedra leads to a negative open framework of FeAPO-CJ51. The structural building units of FeAPO-CJ51 are shown in Fig. 2. The basic composite building unit (CBU) contains eight P atoms and seven metal atoms, which can be seen as two 6 ∗ 1 configuration connected through metal-centered MO6 octahedron. The configuration denoted 6 ∗ 1 by International Zeolite Association (IZA) means that a tetrahedral atom has three bonds with three atoms of 6-ring (6R), forming three quadrilaterals [17]. In the framework of FeAPOCJ51, the basic composite building units are connected in a “head to tail”
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Y. Guo et al. / Inorganic Chemistry Communications 47 (2014) 99–101
Fig. 1. Thermal ellipsoids of FeAPO-CJ51 given at 30% probability, showing the atomic labeling scheme and omitting oxygen atomic labeling for clarity. M(2), M(5), M(3) and M(6) sites are co-occupied by Fe and Al ions.
fashion to form chains running along the [010] direction. The chains from opposite directions are linked together through 4-rings to form undulating layers perpendicular to the [100] direction. The layers are further connected in AAAA stacking sequence through Al\O\P linkages to produce a 3-dimensional open framework of FeAPO-CJ51. It contains interconnecting 8-ring channels along [010] and [001] directions, respectively.
Fig. S1 shows the scanning electron microscopy (SEM) image of the as-synthesized FeAPO-CJ51. Prism-like large single crystals of FeAPOCJ51 can be clearly observed. Fig. S2 shows the powder XRD pattern of FeAPO-CJ51 and the simulated one generated from single-crystal structural data. The good agreement between these XRD patterns proves that the as-synthesized sample is pure phase. ICP and elemental analyses show a (Fe + Al)/P ratio of 7/8, and a Fe/Al ratio of 1/2.5. The respective contents of Al, Fe, P, C, N, and H for FeAPO-CJ51 are 11.30, 9.35, 21.00, 7.99, 4.66, and 2.2 wt.%, respectively. These give the empirical formula (C4H12N2)2[Fe2Al5(PO4)8(H2O)] of FeAPO-CJ51. Thermogravimetric analysis (TGA) of as-synthesized FeAPO-CJ51 shows a total weight loss of 16.5 wt.% from 100 to 800 °C (Fig. S3), which corresponds to the removal of the piperazine and the coordinated water molecule (calcd. 16.2%). XRD indicates that FeAPO-CJ51 is stable at 300 °C. However, its framework collapses above 400 °C after the decomposition of piperazine molecules (Fig. S4). Based on the charge balance, the Fe atom in the framework of FeAPO-CJ51 should be the mixed-valence Fe(II)/Fe(III). The powder 57Fe room temperature Mössbauer spectrum was studied as shown in Fig. 3. The best fit leads to two doublet contributions from Fe2 + and Fe3 +. The isomer shift (IS) values are relative to metallic iron. The results are summarized in Table S3. The area ratio of Fe3+/Fe2+ is 1.04, indicating equal amount of Fe2+ and Fe3+ atoms in the framework of FeAPO-CJ51. Fig. S5 shows the variable–temperature magnetic susceptibility plots of χ m and 1/χm versus temperature for as-synthesized FeAPO-CJ51. The magnetic susceptibilities obey the Curie–Weiss rule [χm = C / (T − θ)], and the respective Weiss constants (θ) and Curie constants (C) are −46.6 K and 5.99 cm3 mol−1 K for FeAPO-CJ51, indicating their antiferromagnetic features. Up to now, three transitional metal elements Fe, Co and Ni have been successfully incorporated into this kind of octahedron–trigonal bipyramid–tetrahedral framework [18,19]. The iron substituted case is particularly interesting because it contains the mixed-valence Fe(II) and Fe(III) atoms. The formation of Fe(II)\O\Fe(III) bond and the unusual coordination environments of iron atoms will cause the interesting electronic properties of FeAPO-CJ51. Further work is undergoing. In conclusion, a new open-framework iron-containing aluminophosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)] (denoted as FeAPO-
Fig. 2. The building scheme of the 3-periodic framework for FeAPO-CJ51. Piperazine molecules are omitted for clarity. Color code: Al, cyan; Fe, yellow; M (Fe/Al), green; P, pink; O, red. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Y. Guo et al. / Inorganic Chemistry Communications 47 (2014) 99–101
Fig. 3. The 57Fe Mössbauer spectroscopy of FeAPO-CJ51 (green and blue lines are fitting doublets and the red line is the overlay of them). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
CJ51), with mixed-valence iron (II, III) and cross-connected 8-ring channels have been synthesized by using piperazine as the template. FeAPOCJ51 shows antiferromagnetic interactions between Fe3+ and Fe2+ atoms in the framework. Acknowledgments This work is supported by the National Basic Research Program of China (Grant No. 2011CB808703) and the National Natural Science Foundation of China (Grant Nos. J1103302 and 21001050). Appendix A. Supplementary material Crystal data, bond lengths (Å) and angles (deg), SEM image, TG analysis, etc. Supplementary data associated with this article can be found in the online version, at http://dx.doi.org/10.1016/j.inoche.2014.07.026. References [1] S. Natarajan, S. Mandak, Open-framework structures of transition-metal compounds, Angew. Chem. Int. Ed. 47 (2008) 4798–4828. [2] R. Murugavel, Amitava Choudhury, M.G. Walawalkar, R. Pothiraja, C.N.R. Rao, Metal complexes of organophosphate esters and open-framework metal phosphates: synthesis, structure, transformations, and applications, Chem. Rev. 108 (2008) 3549–3655. [3] Z.P. Wang, J.H. Yu, R.R. Xu, Needs and trends in rational synthesis of zeolitic materials, Chem. Soc. Rev. 41 (2012) 1729–1741.
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[4] a) J.H. Yu, R.R. Xu, Chiral zeolitic materials: structural insights and synthetic challenges, J. Mater. Chem. 18 (2008) 4021–4030; b) J. Yu, R. Xu, Rational approaches toward the design and synthesis of zeolitic inorganic open-framework materials, Acc. Chem. Res. 43 (2010) 1195–1204. [5] A.K. Cheetham, G. Férey, T. Loiseau, Open-framework inorganic materials, Angew. Chem. Int. Ed. 38 (1999) 3268–3292. [6] K.H. Lii, Y.F. Huang, V. Zima, Syntheses and structures of organically templated iron phosphates, Chem. Mater. 10 (1998) 2599–2609. [7] M. Riou-Cavellec, D. Riou, G. Férey, Magnetic iron phosphates with an open framework, Inorg. Chim. Acta 291 (1999) 317–325. [8] S. Fernande-Armas, J.L. Mesa, J.L. Pizarro, J.S. Garitaonandia, M.I. Arriortua, T. Rojo, (C4N2H12)[FeII0.86FeIII1.14(HPO3)1.39(HPO4)0.47(PO4)0.14 F3]: a fluorophosphate-hydrogen phosphate–phosphate Iron(II, III) mixed-valence organically templated compound, Angew. Chem. Int. Ed. 116 (2004) 995–998. [9] M. Dugal, G. Sankar, R. Raja, J.M. Thomas, Designing a heterogeneous catalyst for the production of adipic acid by aerial oxidation of cyclohexane, Angew. Chem. Int. Ed. 39 (2000) 2310–2313. [10] R. Raja, G. Sankar, J.M. Thomas, Powerful redox molecular sieve catalysts for the selective oxidation of cyclohexane in air, J. Am. Chem. Soc. 121 (1999) 11926–11927. [11] M. Ai, E. Muneyama, A. Kunishige, Effects of methods of preparing iron phosphate and P/Fe compositions on the catalytic performance in oxidative dehydrogenation of isobutyric acid, J. Catal. 144 (1993) 632–635. [12] P. Bonnet, J. Millet, C. Leclercq, Study of a new iron phosphate catalyst for oxidative dehydrogenation of isobutyric acid, J. Catal. 158 (1996) 128–141. [13] P.B. Moore, J. Shen, An X-ray structural study of cacoxenite, a mineral phosphate, Nature 306 (1983) 356–358. [14] L. Peng, J.Y. Li, J.H. Yu, G.H. Li, Q.R. Fang, R.R. Xu, Solvothermal synthesis, structure and Mössbauer spectroscopy of a new mixed-valence iron aluminophosphate [FeII(H2O)2 FeIII 0.8Al1.2(PO4)3]·H3O, C. R. Chim. 8 (2005) 541–547. [15] Synthesis: FeAPO-CJ51 was synthesized under hydrothermal conditions by using piperazine as the structure-directing agent. Typically, iron(II) chloride tetrahydrate (0.35 g) and orthophosphoric acid (0.54 mL, 85 wt.%) were first added into water (10 mL) with stirring for half an hour, followed by the addition of aluminum triisopropoxide (0.6 g) and oxalate (0.9 g). The mixture was stirred for 4 hours and piperazine (1.425 g) was added to give a gel with overall molar composition of 0.6 FeCl2/1.0 Al(iPrO)3/2.7 H3PO4/2.5 H2C2O4/2.5 piperazine/110 H2O. The gel was stirred until it was homogeneous and then sealed in a 25 mL Teflon-lined stainless steel autoclave at 180 °C for 3 days. The yellow prism-like crystals of FeAPOCJ51 were washed with water and dried in air at room temperature. [16] The data were collected on a Rigaku R-AXIS RAPID diffractometer in the range of 1. 40–28.27° at the temperature of 296 ± 2 K using graphite-monochromated MoKα radiation (λ = 0.71073 Å). The structure was solved by direct method and refined by full matrix least-squares technique with the SHELXTL 97 [20] crystallographic software package. All non-H atoms of framework were located from a difference Fourier map and refined anisotropically. Detail crystallographic data of have been deposited at Cambridge Crystallographic Data Center (CCDC-911675). [17] Ch. Baerlocher, L.B. McCusker, D.H. Olson, Atlas of Zeolite Framework Types, Elsevier, Netherlands, 2007.; C. Baerlocher, L.B. McCusker, Database of Zeolite Structures, http://www.izastructure. org/databases/ . [18] L.M. Meyer, R.C. Haushalter, The first octahedral–trigonal bipyramidal–tetrahedral framework oxide: hydrothermal synthesis and structure of K[Ni(H2O)2Al2(PO4)3], Chem. Mater. 6 (1994) 349–350. [19] C. Panz, K. Polborn, P. Behrens, LMU-3: a new cobalt aluminophosphate with exclusively five-coordinated aluminium and octahedrally coordinated cobalt, Inorg. Chim. Acta 269 (1998) 73–82. [20] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112.
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Synthesis and characterization of a new open-framework mixed-valence aluminum–iron phosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)] Yanan Guo a,b, Yuchen Qiu a, Jiyang Li a, Lang Shao a, Xiaowei Song a,⁎ a
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China Laboratory of Environmental Science and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011, China
b
a r t i c l e
i n f o
Article history: Received 10 June 2014 Received in revised form 18 July 2014 Accepted 21 July 2014 Available online 22 July 2014 Keywords: Open framework Aluminophosphate Iron Mixed-valence
a b s t r a c t A new open-framework aluminum–iron phosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)] (denoted as FeAPO-CJ51), with mixed-valence iron (II, III) has been hydrothermally synthesized by using piperazine as the template. The three-dimensional framework of FeAPO-CJ51 is constructed by the connection of metal-centered MOn (M = Fe/Al, n = 4, 5, 6) polyhedra and PO4 tetrahedra, which contains interconnecting 8-ring channels along the [010] and [001] directions. Diprotonated piperazine cations locate in the 8-ring channels to compensate the negative charge of the anionic framework. Mössbauer and magnetic susceptibility measurements show that equal amounts of Fe2+ and Fe3+ are present in FeAPO-CJ51, which undergo the long-range antiferromagnetic interactions. © 2014 Published by Elsevier B.V.
Inorganic open-framework materials are an important class of functional materials owing to their widespread applications as ion exchangers, battery materials, catalysts, nonlinear optics, and gas storage/adsorption materials [1–3]. A large number of open-framework compounds with rich structure and charming properties have been synthesized under hydrothermal or solvothermal conditions [4,5]. The mixed aluminum–iron phosphate open-framework compounds have received considerable interest due to their rich structural diversity [6,7] and other promising properties including magnetic properties [8] and activities in some specific catalytic reactions [9]. For example, Fesubstituted AlPO4-5 calcined at relatively high temperature (823 K) was applied in the selective oxidation of benzene, and showed high selectivity to phenol [10]. Some of the dense ferrophosphates have been used for the selective oxidative dehydrogenation of isobutyric acid into methacrylic acid [11,12]. The mixed aluminum–iron phosphate cacoxenite [13] represents the most remarkable example of this family. Its open framework contains extra large channels of 14.2 Å, in which water molecules are trapped. In aluminum–iron phosphate structures, the oxidation state of Fe atoms are observed as + 3, + 2 or mixed valences, but these Fe atoms are often in the same coordination environments. The reports of metal aluminophosphates contain mixedvalence irons with different coordination states which are limited [14]. In this paper, we present a new 3-D aluminum–iron phosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)](denoted as FeAPO-CJ51) templated by piperazine, which contains interconnecting 8-ring channels along ⁎ Corresponding author. E-mail address: [email protected] (X. Song).
http://dx.doi.org/10.1016/j.inoche.2014.07.026 1387-7003/© 2014 Published by Elsevier B.V.
the [010] and [001] directions, and mixed-valence Fe(II)/Fe(III) atoms. The syntheses, structure, and magnetic properties have been studied. FeAPO-CJ51 was hydrothermally synthesized in the presence of piperazine as the template [15], which was characterized by singlecrystal X-ray diffraction structural analysis [16] and other characterization techniques. Crystallographic data, selected bond lengths and angles for FeAPO-CJ51 are summarized in Tables S1 and S2, respectively. FeAPO-CJ51 crystallizes in the triclinic space group P-1 (No. 2). Its cell dimensions are: a = 9.057(2) Å, b = 12.606(3) Å, c = 14.623(4) Å, α = 89.547(4)°, β = 86.530(4)° and γ = 72.512(4)°. Fig. 1 shows the thermal ellipsoids of FeAPO-CJ51. The crystallographically independent Fe atom occupying Fe(1) site is 4-coordinated and the crystallographically independent Al atom occupying Al(4) and Al(7) sites are 5-coordinated. While other metal sites (M(2), M(5), M(3) and M(6)) are co-occupied by Fe and Al atoms, which present four, five, and six coordinations, with the occupancies of Fe atom of 60%, 15%, 10%, and 15% respectively. The occupancy of Fe atom in each metal site was determined by the refinements using the SHELXTL 97, which is consistent with the bond lengths of Fe/Al\O. Strict alternation of MOn (M = Fe/Al, n = 4, 5, 6) polyhedra and PO4 tetrahedra leads to a negative open framework of FeAPO-CJ51. The structural building units of FeAPO-CJ51 are shown in Fig. 2. The basic composite building unit (CBU) contains eight P atoms and seven metal atoms, which can be seen as two 6 ∗ 1 configuration connected through metal-centered MO6 octahedron. The configuration denoted 6 ∗ 1 by International Zeolite Association (IZA) means that a tetrahedral atom has three bonds with three atoms of 6-ring (6R), forming three quadrilaterals [17]. In the framework of FeAPOCJ51, the basic composite building units are connected in a “head to tail”
100
Y. Guo et al. / Inorganic Chemistry Communications 47 (2014) 99–101
Fig. 1. Thermal ellipsoids of FeAPO-CJ51 given at 30% probability, showing the atomic labeling scheme and omitting oxygen atomic labeling for clarity. M(2), M(5), M(3) and M(6) sites are co-occupied by Fe and Al ions.
fashion to form chains running along the [010] direction. The chains from opposite directions are linked together through 4-rings to form undulating layers perpendicular to the [100] direction. The layers are further connected in AAAA stacking sequence through Al\O\P linkages to produce a 3-dimensional open framework of FeAPO-CJ51. It contains interconnecting 8-ring channels along [010] and [001] directions, respectively.
Fig. S1 shows the scanning electron microscopy (SEM) image of the as-synthesized FeAPO-CJ51. Prism-like large single crystals of FeAPOCJ51 can be clearly observed. Fig. S2 shows the powder XRD pattern of FeAPO-CJ51 and the simulated one generated from single-crystal structural data. The good agreement between these XRD patterns proves that the as-synthesized sample is pure phase. ICP and elemental analyses show a (Fe + Al)/P ratio of 7/8, and a Fe/Al ratio of 1/2.5. The respective contents of Al, Fe, P, C, N, and H for FeAPO-CJ51 are 11.30, 9.35, 21.00, 7.99, 4.66, and 2.2 wt.%, respectively. These give the empirical formula (C4H12N2)2[Fe2Al5(PO4)8(H2O)] of FeAPO-CJ51. Thermogravimetric analysis (TGA) of as-synthesized FeAPO-CJ51 shows a total weight loss of 16.5 wt.% from 100 to 800 °C (Fig. S3), which corresponds to the removal of the piperazine and the coordinated water molecule (calcd. 16.2%). XRD indicates that FeAPO-CJ51 is stable at 300 °C. However, its framework collapses above 400 °C after the decomposition of piperazine molecules (Fig. S4). Based on the charge balance, the Fe atom in the framework of FeAPO-CJ51 should be the mixed-valence Fe(II)/Fe(III). The powder 57Fe room temperature Mössbauer spectrum was studied as shown in Fig. 3. The best fit leads to two doublet contributions from Fe2 + and Fe3 +. The isomer shift (IS) values are relative to metallic iron. The results are summarized in Table S3. The area ratio of Fe3+/Fe2+ is 1.04, indicating equal amount of Fe2+ and Fe3+ atoms in the framework of FeAPO-CJ51. Fig. S5 shows the variable–temperature magnetic susceptibility plots of χ m and 1/χm versus temperature for as-synthesized FeAPO-CJ51. The magnetic susceptibilities obey the Curie–Weiss rule [χm = C / (T − θ)], and the respective Weiss constants (θ) and Curie constants (C) are −46.6 K and 5.99 cm3 mol−1 K for FeAPO-CJ51, indicating their antiferromagnetic features. Up to now, three transitional metal elements Fe, Co and Ni have been successfully incorporated into this kind of octahedron–trigonal bipyramid–tetrahedral framework [18,19]. The iron substituted case is particularly interesting because it contains the mixed-valence Fe(II) and Fe(III) atoms. The formation of Fe(II)\O\Fe(III) bond and the unusual coordination environments of iron atoms will cause the interesting electronic properties of FeAPO-CJ51. Further work is undergoing. In conclusion, a new open-framework iron-containing aluminophosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)] (denoted as FeAPO-
Fig. 2. The building scheme of the 3-periodic framework for FeAPO-CJ51. Piperazine molecules are omitted for clarity. Color code: Al, cyan; Fe, yellow; M (Fe/Al), green; P, pink; O, red. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Y. Guo et al. / Inorganic Chemistry Communications 47 (2014) 99–101
Fig. 3. The 57Fe Mössbauer spectroscopy of FeAPO-CJ51 (green and blue lines are fitting doublets and the red line is the overlay of them). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
CJ51), with mixed-valence iron (II, III) and cross-connected 8-ring channels have been synthesized by using piperazine as the template. FeAPOCJ51 shows antiferromagnetic interactions between Fe3+ and Fe2+ atoms in the framework. Acknowledgments This work is supported by the National Basic Research Program of China (Grant No. 2011CB808703) and the National Natural Science Foundation of China (Grant Nos. J1103302 and 21001050). Appendix A. Supplementary material Crystal data, bond lengths (Å) and angles (deg), SEM image, TG analysis, etc. Supplementary data associated with this article can be found in the online version, at http://dx.doi.org/10.1016/j.inoche.2014.07.026. References [1] S. Natarajan, S. Mandak, Open-framework structures of transition-metal compounds, Angew. Chem. Int. Ed. 47 (2008) 4798–4828. [2] R. Murugavel, Amitava Choudhury, M.G. Walawalkar, R. Pothiraja, C.N.R. Rao, Metal complexes of organophosphate esters and open-framework metal phosphates: synthesis, structure, transformations, and applications, Chem. Rev. 108 (2008) 3549–3655. [3] Z.P. Wang, J.H. Yu, R.R. Xu, Needs and trends in rational synthesis of zeolitic materials, Chem. Soc. Rev. 41 (2012) 1729–1741.
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