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Arenedisulfonate-4d–4f 3D heterometallic coordination polymers constructed from 2,7-naphthalenedisulfonate and isonicotinic acid: Structure, luminescence, and magnetic properties
Inorganic Chemistry Communications 40 (2014) 151–156
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Arenedisulfonate-4d–4f 3D heterometallic coordination polymers constructed from 2,7-naphthalenedisulfonate and isonicotinic acid: Structure, luminescence, and magnetic properties☆ Wei-Ping Xie a, Ning Wang b, Yi Long b, Xing-Rui Ran a, Jin-Ying Gao a, Chu-Jun Chen a, Shan-Tang Yue a,⁎, Yue-Peng Cai a a b
School of Chemistry and Environment, South China Normal University, Guangzhou 510006, PR China School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798, Singapore
a r t i c l e
i n f o
Article history: Received 11 October 2013 Accepted 21 November 2013 Available online 28 November 2013 Keywords: 4d–4f coordination polymers Topology Luminescence Magnetism
a b s t r a c t The first example of 3D heterometallic 4d–4f 2,7-naphthanlenedisulfonate compounds [LnAg2(2,7-NDS)(IN)3] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy(5); 2,7-NDS = 2,7-naphthanlenedisulfonate; IN = isonicotinic acid) has been synthesized via hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analyses, FT-IR spectroscopy, powder X-ray diffraction(PXRD) and thermogravimetric analyses (TGA). X-Ray structural analysis reveals that compounds 1–5 exhibit same well-organized 3D coordination frameworks that are built up by 2D elliptical cylinder shaped [LnAg 2(2,7-NDS)(IN)3] layers which are constructed by 1D anionic chains [Ln(2,7-NDS)(IN)3]2 − linking the adjacent Ag(I) ions, and [LnAg(μ2-O)2] units, possessing a 7-connected topology with the Schläfli symbol of {33;411;56;6}. Furthermore, the luminescence properties of compounds 2 and 4 and the magnetic properties of compounds 3 and 5 were investigated. © 2013 The Authors. Published by Elsevier B.V. All rights reserved.
The past decades witnessed tremendous development of the field of metal–organic frameworks (MOFs) owing to their potential applications in magnetism, photoluminescence, sorption, catalysis, chemical separation, ion exchange [1–6], as well as their fascinating topologies and intriguing architectures. Generally speaking, the nature of ligands, metal ions, reaction conditions, and solvents is the main factor to influence the ultimate complex architectures and properties, especially the selection of ligands [7]. In recent years, arenedisulfonates have sparked great interest for chemists to select them as the excellent candidates in constructing functional coordination polymers for their rigid structure, alterable coordination modes of SO− 3 ranging from μ1 to μ6 [8], multiple H-bonding acceptors by oxygen atoms in sulfonate groups which easily build high-dimensional supramolecular architectures [9], and exciting properties of their coordination complexes in catalysis, photoluminescence, magnetism, ion selective et al. [8a,10]. However, up to now, most of the coordination compounds with arenedisulfonates ligands reported are single transition metal or rare earth metal complexes [11], the lanthanide − transition heterometallic arenedisulfonates complexes are still quite scarce. As far as we know, there are only two examples of d–f heterometallic
☆ This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial-No Derivative Works License, which permits noncommercial use, distribution, and reproduction in any medium, provided the original author and source are credited. ⁎ Corresponding author. Tel./fax: +86 20 39310187. E-mail address: [email protected] (S.-T. Yue).
arenedisulfonates system, one is A. M. Fogg et al. reported the Mo–Ln heterometallic compounds built by 1,5-naphthalenedisulfonate and 2,6naphthalenedisulfonate [12], the other is our group reported the Cu–Ln heterometallic compounds constructed by 2,6-naphthalenedisulfonate [10d]. In addition, in these two examples, only lanthanide ions coordinate to arenedisulfonate ligands. Now there is no report about transition metal and lanthanide heterometallic coordination polymers constructed from 2,7-naphthalenedisulfonate ligand. Therefore the construction of highdimensional heteronuclear arenedisulfonates coordination frameworks with versatility and interesting topologies is still a challenging task due to the following reasons: (i) the coordinating ability of organosulfonates is usually weak [13], so that it is difficult for them to bind metal ions by directional covalent bonds. (ii) the coordination numbers of lanthanide ions are variable and high [14], and lanthanide and transition metal ions have a competition during connecting to ligands [15]. Fortunately, the characteristics of lanthanide and transition metal ions have different affinities for N and O donors [16], that urge us to synthesize novel heterometallic coordination frameworks with arenedisulfonates by introducing an auxiliary ligand. With this in mind, we employed 2,7-naphthalenedisulfonate (2,7NDS) and isonicotinic acid (IN) as bridging ligands, silver nitrate and lanthanide nitrate as d and f metal sources into the 4d–4f system. The use of isonicotinic acid as a co-ligand has the following considerations: (i) it is a multifunctional ligand with the mixed coordination sites (O atom and N atom), O atom prefers to bond to Ln ions, while N atom possesses a strong tendency to coordinate to transition metal ions such as Cu(I) or Ag(I) ion. (ii) it is a rigid and linear ligand, which
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can be fittingly used as the pillars to support high dimensional metal– organic frameworks [17]. By this strategy, five novel 3D heterometallic naphthanlenedisulfonate compounds [LnAg2 (2,7-NDS)(IN) 3 ] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy(5); 2,7-NDS = 2,7-naphthanlenedisulfonate; IN = isonicotinic acid) were synthesized under hydrothermal conditions [18]. In the structure, the lanthanide and transition ions all coordinate to 2,7-NDS ligands which are a rare case among arenedisulfonate architectures. The IR spectra of all products show similarities. The 3500–3190 cm− 1 range was assigned to the O\H stretching vibrations of water molecules in complexes. There are no strong absorption peaks around 1700 cm− 1 illustrating complete deprotonation of carboxyl groups, in agreement with the results of single crystal X-ray diffraction [19]. The strong peaks of carboxyl groups in 1–5 appear in the region of 1608–1551 cm− 1 (antisymmetric stretching vibrations) and 1408–1380 cm− 1 (symmetric stretching vibrations). Characteristic antisymmetric νas(SO− 3 ) and symmetric νs (SO − 3 ) and modes for 2,7-NDS were observed in the region of 1241–1169 cm− 1 and 1097–1020 cm− 1, respectively [20]. X-ray crystal structure analysis reveals [21] that compounds 1–5 are isomorphic, all crystallizing in the orthorhombic space group Pbca and possessing 3D coordination frameworks with 2D elliptical cylinder shaped [LnAg2(2,7-NDS)(IN)3] layers and [LnAg(μ2-O)2] units, therefore, only the structure of 1 is described in detail here. As shown in Fig. 1, the asymmetry unit of compound 1 consists of one Sm(III) ion, two Ag(I) ions, one independent 2,7-NDS ligand and three crystallographically unique IN ligands. The Sm(III) ion is coordinated by eight oxygen atoms from six IN− ions and two 2,7-NDS ligands in a distorted dicapped trigonal prismatic geometry. The Sm\O bond distances range from 2.342(7) to 2.510(6) Å, which are comparable to those of other samarium − carboxylate and samarium − sulfonate compounds [17,20]. The Sm–O (1), Eu–O (2), Gd–O (3), Tb–O (4) and Dy–O (5) distances decrease gradually as listed in table S1 because of the lanthanide contraction effect [22]. The bond angles of O\Sm\O range from 70.6(3)° to 146.7(3)°. As it is not appropriate to use the terms syn and anti to describe the coordination mode of metal arenedisulfonates, the torsion angles of C–S–O–Sm are used [23]. In 1, the torsion angles of C(3)-S(1)-O(1)-Sm(1), C(3)-S(1)-O(2)Sm(1), and C(9)-S(2)-O(6)-Ag(2) are 156.958°, 93.818(735)°, and 112.660(409)°, respectively. As far as the Ag(I) ions are concerned, two Ag(I) ions adopt different coordination modes. Ag1 is two-coordinated while Ag 2 is four-coordinated. The Ag1 is coordinated in a linear fashion by two nitrogen atoms from two different IN− ions with Ag–N distances of 2.143(8) Å and 2.153(3) Å, and bond angle of 165.3(3)°. Nevertheless, the four-coordinated Ag2 exhibits a distorted tetrahedron coordination geometry by one oxygen atom from one IN− ion, two oxygen atoms from two 2,7-NDS ligands and one nitrogen atom from one IN− ion. The Ag2–O distances vary from
Fig. 1. Coordination environment of Sm and Ag atoms in 1. All H atoms are omitted for clarity. Symmetry codes: a) 0.5 − x, 0.5 + y, z; b) 0.5 − x, − 0.5 + y, z; c) 0.5 + x, 0.5 − y, -z; d) 1 − x, 0.5 + y, 0.5 − z.
2.479(8)–2.545(11) Å and the Ag2\N3 bond length is 2.226(3) Å. The bond angles of O-Ag2-N fall in the range of 92.1(3)°–160.0(3)°. The 2,7-NDS ligand in 1 only adopts one coordinated mode (μ4) with one of the 7-sulfonate oxygen atoms coordinating to one Ag(I) center and the 2-sulfonate oxygen atoms coordinating to two different Sm(III) ions and one Ag(I) center via a μ3–η1:η2 fashion (Scheme 1a). Each 2,7-NDS ligand leaves three free oxygen atoms. The IN ligand in 1 acts two kinds of coordination fashions: (i) the nitrogen atom coordinates to one Ag(I) center and the carboxylate oxygen atoms link to two Sm(III) ions in a bismonodentate mode (Scheme 1b). (ii) only minor difference between fashion(i) and fashion(ii) is that one of the carboxylate oxygen atoms also coordinates to one Ag(I) center (Scheme 1c). On the basis of such coordination modes of 2,7-NDS and IN ligand, as well as the characteristics of lanthanide metal ions with the affinity for oxygen donors, 1D Sm-based chain with Sm\O\C\O\Sm and Sm\O\S\O\Sm connectivity containing 1D lantern-like four strand helix is built up along the b axis direction, and the distance between neighboring Sm(III) ions in one chain is 4.764 Å (Fig. 2a). Notably, the most important aspect is that this arrangement exactly offers active nitrogen atoms of IN ligands and oxygen atoms of 2,7-NDS ligands to coordinate to adjacent Ag(I) ions to construct 2D 4d–4f elliptical cylinder shaped heterometallic layers along the ac plane (Fig. 2b) [24]. As indicated in Fig. 2b, there are two kinds of bow-like bridges IN–Ag–IN with the angle of N–Ag–N 165.3(3)° and IN–Ag-(2,7-NDS) with the angle of N–Ag–O 92.1(3)° in the upper and lower arc-like layers of 2D heterometallic layers [17a]. Due to carboxylic oxygen atom O11 and sulfonic oxygen atom O2 coordinating to both Sm center and Ag2 center separately with the chelating-bridging mode, the adjacent 2D layers are subtly assembled into a well-organized 3D network coordination framework by [SmAg(μ 2 -O)2 ] units with the Sm–O–Ag angle of 104.210(328)° and 105.327(263)° (Fig. 3). In such a 3D network structure, the ligand 2,7-NDS successfully chelated to lanthanide and transition metal ions and improved the dimensions of the aimed complexes, which is a rare example of covalently bonded 3D 4d–4f heteronuclear networks containing elliptical cylinder shaped layers built by organodisulfonate.
Scheme 1. Coordination modes of 2,7-NDS and IN ligands.
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Fig. 2. (a) View of 1D anionic chain [Ln(2,7-NDS)(IN)3]2− containing a lantern-like four strand helical chain along the b axis direction in compound 1. (b) 2D 4d–4f heteronuclear layer assembled by 1D anionic chain [Ln(2,7-NDS)(IN)3]2− linking the adjacent Ag(I) ions. (c) View of the elliptical cylinder shaped 2D 4d–4f heteronuclear layer.
To better understand the complicated framework, the network topology of compound 1 is analyzed. We define Sm(III) centers as 7connected nodes, IN–Ag–IN and IN–Ag-(2,7-NDS) as bridge linkers. The separations for Sm–Sm are 4.76 Å, 12.234 Å, 12.261 Å and 17.333 Å. Hence, according to the calculation of TOPOS 4.0, the framework of 1 belongs to 7-connected network with the Schläfli symbol of (33;411;56;6) (Fig. 4). Compounds 1–5 were also characterized by powder X-ray diffraction at room temperature in the range of 2θ = 5–50° as shown in Fig. S1. The positions of the diffraction peaks in simulated and experimental patterns correspond well indicating the phase purity of the asprepared products. On account of the similarity of the structures for 1–5, compounds 2, 3 and 4 were selected for thermogravimetric analyses (TGA) to examine the thermal stability of all compounds and their TGA curves are shown
in Fig. S2. The thermogravimetric analyses were done from 30 to 800 °C at a heating rate of 10 °C/min in dry air atmosphere. These frameworks can be stable up to about 350 °C, suggesting relatively high thermal stability of these compounds. Such a thermal stability of 2, 3 and 4 may be attributed to the linkages of IN–Ag–IN and IN–Ag-(2,7-NDS) chains. Then consecutive weight loss from 375 °C is probably caused by the decomposition of the 2,7-NDS and IN ligands, resulting in the collapse of whole 3D frameworks. Because of the excellent luminescent properties of lanthanide complexes, the solid-state photoluminescence of compounds 2 and 4 was measured at room temperature. When excited at 393 nm, the europium compound of 2 emits red fluorescence and exhibits characteristic bands at 579 nm (5 D 0 → 7F 0), 587 and 594 nm (5D0 → 7F1), 613 nm (5D0 → 7F2), 653 nm (5D0 → 7F3), and 704 nm (5D0 → 7F4), arising from the transition of 5D0 → 7FJ (J = 0 → 4) of
Fig. 3. The adjacent elliptical cylinder shaped 2D layers were assembled into 3D coordination frameworks by [SmAg(μ2-O)2] units. (The IN–Ag–IN bridges were omitted for clarity).
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Fig. 4. View of the 3D uninodal 7-connected topological networks of compound 1.
the Eu(III) ions. 5 D 0 → 7 F1 and 5D 0 → 7 F 2 are the most intense transitions(Fig. 5). The 5 D 0 → 7 F1 transition is a magnetic dipole transition, and its intensity is relatively unaffected by the local environment around Eu(III) ions. However, the 5D0 → 7F2 transition is an electric dipole transition, and is hypersensitive to chemical bonds in the vicinity of Eu(III) ions. Furthermore, the intensity of the 5 D 0 → 7 F2 transition decreases as the site symmetry of Eu (III) increases. Therefore, this disparity allows the use of the relative intensities of 5D0 → 7F2 transition and 5D0 → 7F1 transition to probe the symmetry of the Eu(III) centers [25]. For compound 2, the intensity ratio I (5D0 → 7F2)/I (5D0 → 7F1) is ca. 0.76, approximating 0.67, a typical value for a centrosymmetric central Eu(III) ion, which suggests that Eu(III) ions in 2 have a centrosymmetric coordination environment in agreement with the results of the single-crystal X-ray analysis. Compound 4 yields green light when excited at 301 nm, and it gives the characteristic emission of 5 D 4 /7 F J (J = 3 → 6) of the Tb(III) ions (Fig. 6). Two intense emission bands at 544 nm and 593 nm correspond to 5D4 → 7F5 and 5D4 → 7F4 respectively, while the weaker emission bands at 488 nm and 616 nm originate from 5 D4 → 7F6 and 5D4 → 7F3. The direct-current magnetic susceptibility for compounds 3 and 5 was measured in the range of 2 to 300 K under the field of 1000 Oe, as plots of χM vs T and 1/χM vs T as shown in Fig. 7. In the crystal structure of compounds 3 and 5, the 1D Ln-2,7-NDS-Ln chain with ~4.764 Å Ln⋯Ln bond length was separated effectively. Thus the magnetic coupling effects were mainly ascribed to the Ln-cation interactions within the 1D Ln-2,7-NDS-Ln chains. For compound 3, the magnetic
Fig. 5. Solid-state emission spectra of 2 at room temperature (Ex = 393 nm).
Fig. 6. Solid-state emission spectra of 4 at room temperature (Ex = 301 nm).
susceptibility could be simulated by Fisher expressions for infinite chain with SGd = 7/2 [26]. χM ¼
Ng2 β2 SðS þ 1Þ 1 þ u JSðS þ 1Þ kB T − with u ¼ coth : 3kB T 1−u kB T JSðS þ 1Þ
Fig. 7. Plots of χM vs T and 1/χM vs T for compound 3 (a) and 5 (b).
W.-P. Xie et al. / Inorganic Chemistry Communications 40 (2014) 151–156
The best fitting result is g = 2.00, J = − 1.17 × 10−2 cm−1 with 2
∑ðχ calc −χ obs Þ ). Moreover, ∑χ obs 2 the 1/χ M data obey the Curie–Weiss law χ M = C/(T − θ), with C = 8.13 cm 3 K mol − 1 , θ = − 0.19 K. The negative J and θ value indicates the antiferromagnetic coupling between the Gd(III) cations within the 1D Ln-2,7-NDS-Ln chain. However, for compound 5, it is hard to simulate the magnetic data with the isotropic fisher mode due to the strong orbit contributions for Dy(III) cations. But the 1/χ M data of compound 5 also obey the Curie–Weiss law with C = 14.17 cm3 K mol− 1 and θ = − 3.38 K. The negative θ value may also indicate the antiferromagnetic coupling in the 1D Dy-2,7-NDS-Dy chain. In conclusion, five novel 3D 4d–4f heterometallic coordination polymers have been synthesized through hydrothermal reactions by using 2,7-naphthalenedisulfonate as the main ligand and isonicotinic acid as the co-ligand. These isostructural 3D coordination frameworks were built up by 2D elliptical cylinder shaped [LnAg2(2,7-NDS)(IN)3] layers which are constructed by 1D anionic chains [Ln(2,7-NDS)(IN)3]2 − linking the adjacent Ag(I) ions, and [LnAg(μ2-O)2] units possessing a 7-connected topology with the Schläfli symbol of {33;411;56;6}. This work may enrich the family of coordination chemistry of the arenedisulfonate ligands. In addition, Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence and complexes 3 and 5 show antiferromagnetic behaviours. agreement factor R = 2.58 × 10−5 (R=
Acknowledgments This work was financially supported by the National Nature Science Foundation of China (20971047, U0734005 and 21271076), Key Program of Guangdong Universities Science and Technology innovation (cxzd1020), and Planning Program of Guangzhou City Science and Technology (2013J4100049).
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Appendix A. Supplementary material CCDC 926932–926934, 926937–926938 contain the supplementary crystallographic data for 1–5. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif, or from the Cambridge Crystallographic Data Centre, 12 Union Road, CambridgeCB2 1EZ, UK[Fax:+44(1223)336033; E-mail: [email protected]]. Supplementary data to this article can be found online at http://dx.doi.org/10.1016/j.inoche.2013.11. 029.
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(c) X.F. Li, R. Cao, Syntheses, structure and properties of three-dimensional pillared-layer Ag(I)–Ln(III) heterometallic coordination polymers based on mixed isonicotinate and hemimellitate ligands, J. Solid State Chem. 196 (2012) 182–186. [18] Synthesis of compounds 1–5: a mixture of 2,7-naphthalenedisulfonate sodium salt (0.1661 g, 0.5 mmol), isonicotinic acid (0.127 g, 1.0 mmol), Sm(NO3)·6H2O for 1 (0.1333 g, 0.3 mmol), Eu(NO3)·6H2O for 2 (0.1338 g, 0.3 mmol), Gd(NO3)·6H2O for 3 (0.1353 g, 0.3 mmol), Tb(NO3)·6H2O for 4 (0.1359 g, 0.3 mmol), Dy(NO3)·6H2O for 5 (0.1369 g, 0.3 mmol), AgNO3 (0.0510 g, 0.3 mmol) were dissolved in 8 mL of H2O, then heated to 180 °C for 72 h in a 23 mL Teflon-lined stainless-steel autoclave. After cooling to room temperature at a rate of 5 °C/h, yellow block crystals were collected manually, washed with distilled water for several times and dried in air. For 1, Yield 45% based on Sm. Anal. Calcd for C28H18Ag2N3O12S2Sm: C 32.98, H 1.77, N 4.13%. Found: C 32.97, H 1.76, N 4.11%. IR data (KBr, cm−1): 3469(s), 3195 (s), 1604(s), 1548(m), 1406(s), 1388(s), 1240(m), 1170(m), 1096(m), 1021(m), 853(w), 777(m), 691(m), 569(m). For 2, Yield 44% based on Eu Anal. Calcd for C28H18Ag2N3O12S2Eu: C 32.93, H 1.76, N 4.13%. Found: C 32.92, H 1.75, N 4.12%. IR data (KBr, cm−1): 3443(s), 3202(s), 1606(s), 1548(m), 1406(s), 1382(s), 1240(m), 1169(m), 1095(m), 1020(m), 855(w), 775(m), 690(m), 567(m). For 3, Yield 42% based on Gd. Anal. Calcd for C28H18Ag2N3O12S2Gd: C 32.76, H 1.76, N 4.10%. Found: C 32.75, H 1.76, N 4.09%. IR data (KBr, cm−1): 3445(s), 3203(s), 1607(s), 1549(m), 1406(s), 1383(s), 1230(m), 1170(m), 1096(m), 1021(m), 849(w), 776(w), 691(m), 567(m). For 4, Yield 41% based on Tb. Anal. Calcd for C28H18Ag2N3O12S2Tb: C 32.71, H 1.75, N 4.09%. Found: C 32.70, H 1.74, N 4.08%. IR data (KBr, cm−1): 3463(s), 3199(s), 1607(s), 1549(m), 1407(s), 1385(s), 1228(m), 1171(m), 1096(m), 1022(m), 851(w), 777(m), 690(m), 568(m). For 5, Yield 40% based on Dy. Anal. Calcd for C28H18Ag2N3O12S2Dy: C 32.60, H 1.75, N 4.07%. Found: C 32.59, H 1.76, N 4.05%. FT-IR (KBr, cm−1): 3435(s), 3200(s), 1608(s), 1551(m), 1406(s), 1384(s), 1229(m), 1173(m), 1097(m), 1022(m), 849(w), 776(m), 691(m), 566 (m). [19] L.J. Bellamy, The infrared spectra of complex molecules, Wiley, New York, 1958. 258. [20] Q.Y. Liu, W.F. Wang, J.K. Tang, Diversity of lanthanide(III)–organic extended frameworks with a 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid ligand: syntheses, structures, and magnetic and luminescent properties, Inorg. Chem. 51 (2012) 2381–2392.
[21] Crystal data for 1: Orthorhombic, Pbca, a = 17.8453(18) Å, b = 9.5012(10) Å, c = 34.507(4) Å, α = 90° β = 90° γ = 90° V = 5850.7(11) Å3, Z = 8, Dc = 2.313, F(000) = 3928.0, GOF = 1.069, R1(I N 2σ(I)) = 0.0547, wR2 (all data) = 0.1622. 2: Orthorhombic, Pbca, a = 17.847(2) Å, b = 9.4180(12) Å, c = 34.602(4) Å, α = 90° β = 90° γ = 90° V = 5816.0(12) Å3, Z = 8, Dc = 2.330, F(000) = 3936.0, GOF = 1.142, R1(I N 2σ(I)) = 0.0431, wR2 (all data) = 0.1016. 3: Orthorhombic, Pbca, a = 17.928(3) Å, b = 9.4592(14) Å, c = 34.521(5) Å, α = 90 ° β = 90° γ = 90° V = 5854.1(15) Å3, Z = 8, Dc = 2.327, F(000) = 3944.0, GOF = 1.099, R1(I N 2σ(I)) = 0.0601, wR2 (all data) = 0.1720. 4: Orthorhombic, Pbca, a = 17.9026(19) Å, b = 9.4035(10) Å, c = 34.477(4)Å, α = 90° β = 90° γ = 90° V = 5804.1(11) Å3, Z = 8, Dc = 2.351, F(000) = 3952.0, GOF = 1.062, R1(I N 2σ(I)) = 0.0517, wR2 (all data) = 0.1529. 5: Orthorhombic, Pbca, a = 17.906(2) Å, b = 9.4075(11) Å, c = 34.360(4) Å, α = 90 ° β = 90° γ = 90 ° V = 5788.0(12) Å3, Z = 8, Dc = 2.366, F(000) = 3960.0, GOF = 1.057, R1(I N 2σ(I)) = 0.0580, wR2 (all data) = 0.1689. [22] J.X. Liu, Y.F. Hu, T. Zhu, Coordination complexes based on pentacyclohexanocucurbit [5] uril and lanthanide(III) ions: lanthanide contraction effect induced structural variation, CrystEngComm 14 (2012) 6983–6989. [23] (a) C.H. Chen, J.W. Cai, X.M. Chen, Synthesis and crystal structures of four nickel(II) 1,5-naphthalenedisulfonate compounds, J. Chem. Crystallogr. 31 (2001) 271–280; (b) J.W. Cai, M.L. Lin, Selective amine intercalation behavior of [Cd(1,5-nds)(H2O)2, J. Mater. Chem. 13 (2003) 1806–1811. [24] L. Liang, G. Peng, H. Deng, A new family of 3d–4f heterometallic tetrazole-based coordination frameworks: in situ tetrazole ligand synthesis, structure, luminescence, and magnetic properties, Cryst. Growth Des. 12 (2012) 1151–1158. [25] (a) C. Serre, C. Thouvenot, Synthesis, characterisation and luminescent properties of a new three-dimensional lanthanide trimesate: M((C6H3)–(CO2)3) (M = Y, Ln) or MIL-78, J. Mater. Chem. 14 (2004) 1540–1543; (b) M.D. Allendorf, C.A. Bauer, Luminescent metal–organic frameworks, Chem. Soc. Rev. 38 (2009) 1330–1352. [26] M.E. Fisher, Magnetism in one-dimensional systems—the Heisenberg Model for infinite spin, Am. J. Phys. 32 (1964) 343.
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Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Arenedisulfonate-4d–4f 3D heterometallic coordination polymers constructed from 2,7-naphthalenedisulfonate and isonicotinic acid: Structure, luminescence, and magnetic properties☆ Wei-Ping Xie a, Ning Wang b, Yi Long b, Xing-Rui Ran a, Jin-Ying Gao a, Chu-Jun Chen a, Shan-Tang Yue a,⁎, Yue-Peng Cai a a b
School of Chemistry and Environment, South China Normal University, Guangzhou 510006, PR China School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798, Singapore
a r t i c l e
i n f o
Article history: Received 11 October 2013 Accepted 21 November 2013 Available online 28 November 2013 Keywords: 4d–4f coordination polymers Topology Luminescence Magnetism
a b s t r a c t The first example of 3D heterometallic 4d–4f 2,7-naphthanlenedisulfonate compounds [LnAg2(2,7-NDS)(IN)3] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy(5); 2,7-NDS = 2,7-naphthanlenedisulfonate; IN = isonicotinic acid) has been synthesized via hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analyses, FT-IR spectroscopy, powder X-ray diffraction(PXRD) and thermogravimetric analyses (TGA). X-Ray structural analysis reveals that compounds 1–5 exhibit same well-organized 3D coordination frameworks that are built up by 2D elliptical cylinder shaped [LnAg 2(2,7-NDS)(IN)3] layers which are constructed by 1D anionic chains [Ln(2,7-NDS)(IN)3]2 − linking the adjacent Ag(I) ions, and [LnAg(μ2-O)2] units, possessing a 7-connected topology with the Schläfli symbol of {33;411;56;6}. Furthermore, the luminescence properties of compounds 2 and 4 and the magnetic properties of compounds 3 and 5 were investigated. © 2013 The Authors. Published by Elsevier B.V. All rights reserved.
The past decades witnessed tremendous development of the field of metal–organic frameworks (MOFs) owing to their potential applications in magnetism, photoluminescence, sorption, catalysis, chemical separation, ion exchange [1–6], as well as their fascinating topologies and intriguing architectures. Generally speaking, the nature of ligands, metal ions, reaction conditions, and solvents is the main factor to influence the ultimate complex architectures and properties, especially the selection of ligands [7]. In recent years, arenedisulfonates have sparked great interest for chemists to select them as the excellent candidates in constructing functional coordination polymers for their rigid structure, alterable coordination modes of SO− 3 ranging from μ1 to μ6 [8], multiple H-bonding acceptors by oxygen atoms in sulfonate groups which easily build high-dimensional supramolecular architectures [9], and exciting properties of their coordination complexes in catalysis, photoluminescence, magnetism, ion selective et al. [8a,10]. However, up to now, most of the coordination compounds with arenedisulfonates ligands reported are single transition metal or rare earth metal complexes [11], the lanthanide − transition heterometallic arenedisulfonates complexes are still quite scarce. As far as we know, there are only two examples of d–f heterometallic
☆ This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial-No Derivative Works License, which permits noncommercial use, distribution, and reproduction in any medium, provided the original author and source are credited. ⁎ Corresponding author. Tel./fax: +86 20 39310187. E-mail address: [email protected] (S.-T. Yue).
arenedisulfonates system, one is A. M. Fogg et al. reported the Mo–Ln heterometallic compounds built by 1,5-naphthalenedisulfonate and 2,6naphthalenedisulfonate [12], the other is our group reported the Cu–Ln heterometallic compounds constructed by 2,6-naphthalenedisulfonate [10d]. In addition, in these two examples, only lanthanide ions coordinate to arenedisulfonate ligands. Now there is no report about transition metal and lanthanide heterometallic coordination polymers constructed from 2,7-naphthalenedisulfonate ligand. Therefore the construction of highdimensional heteronuclear arenedisulfonates coordination frameworks with versatility and interesting topologies is still a challenging task due to the following reasons: (i) the coordinating ability of organosulfonates is usually weak [13], so that it is difficult for them to bind metal ions by directional covalent bonds. (ii) the coordination numbers of lanthanide ions are variable and high [14], and lanthanide and transition metal ions have a competition during connecting to ligands [15]. Fortunately, the characteristics of lanthanide and transition metal ions have different affinities for N and O donors [16], that urge us to synthesize novel heterometallic coordination frameworks with arenedisulfonates by introducing an auxiliary ligand. With this in mind, we employed 2,7-naphthalenedisulfonate (2,7NDS) and isonicotinic acid (IN) as bridging ligands, silver nitrate and lanthanide nitrate as d and f metal sources into the 4d–4f system. The use of isonicotinic acid as a co-ligand has the following considerations: (i) it is a multifunctional ligand with the mixed coordination sites (O atom and N atom), O atom prefers to bond to Ln ions, while N atom possesses a strong tendency to coordinate to transition metal ions such as Cu(I) or Ag(I) ion. (ii) it is a rigid and linear ligand, which
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can be fittingly used as the pillars to support high dimensional metal– organic frameworks [17]. By this strategy, five novel 3D heterometallic naphthanlenedisulfonate compounds [LnAg2 (2,7-NDS)(IN) 3 ] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy(5); 2,7-NDS = 2,7-naphthanlenedisulfonate; IN = isonicotinic acid) were synthesized under hydrothermal conditions [18]. In the structure, the lanthanide and transition ions all coordinate to 2,7-NDS ligands which are a rare case among arenedisulfonate architectures. The IR spectra of all products show similarities. The 3500–3190 cm− 1 range was assigned to the O\H stretching vibrations of water molecules in complexes. There are no strong absorption peaks around 1700 cm− 1 illustrating complete deprotonation of carboxyl groups, in agreement with the results of single crystal X-ray diffraction [19]. The strong peaks of carboxyl groups in 1–5 appear in the region of 1608–1551 cm− 1 (antisymmetric stretching vibrations) and 1408–1380 cm− 1 (symmetric stretching vibrations). Characteristic antisymmetric νas(SO− 3 ) and symmetric νs (SO − 3 ) and modes for 2,7-NDS were observed in the region of 1241–1169 cm− 1 and 1097–1020 cm− 1, respectively [20]. X-ray crystal structure analysis reveals [21] that compounds 1–5 are isomorphic, all crystallizing in the orthorhombic space group Pbca and possessing 3D coordination frameworks with 2D elliptical cylinder shaped [LnAg2(2,7-NDS)(IN)3] layers and [LnAg(μ2-O)2] units, therefore, only the structure of 1 is described in detail here. As shown in Fig. 1, the asymmetry unit of compound 1 consists of one Sm(III) ion, two Ag(I) ions, one independent 2,7-NDS ligand and three crystallographically unique IN ligands. The Sm(III) ion is coordinated by eight oxygen atoms from six IN− ions and two 2,7-NDS ligands in a distorted dicapped trigonal prismatic geometry. The Sm\O bond distances range from 2.342(7) to 2.510(6) Å, which are comparable to those of other samarium − carboxylate and samarium − sulfonate compounds [17,20]. The Sm–O (1), Eu–O (2), Gd–O (3), Tb–O (4) and Dy–O (5) distances decrease gradually as listed in table S1 because of the lanthanide contraction effect [22]. The bond angles of O\Sm\O range from 70.6(3)° to 146.7(3)°. As it is not appropriate to use the terms syn and anti to describe the coordination mode of metal arenedisulfonates, the torsion angles of C–S–O–Sm are used [23]. In 1, the torsion angles of C(3)-S(1)-O(1)-Sm(1), C(3)-S(1)-O(2)Sm(1), and C(9)-S(2)-O(6)-Ag(2) are 156.958°, 93.818(735)°, and 112.660(409)°, respectively. As far as the Ag(I) ions are concerned, two Ag(I) ions adopt different coordination modes. Ag1 is two-coordinated while Ag 2 is four-coordinated. The Ag1 is coordinated in a linear fashion by two nitrogen atoms from two different IN− ions with Ag–N distances of 2.143(8) Å and 2.153(3) Å, and bond angle of 165.3(3)°. Nevertheless, the four-coordinated Ag2 exhibits a distorted tetrahedron coordination geometry by one oxygen atom from one IN− ion, two oxygen atoms from two 2,7-NDS ligands and one nitrogen atom from one IN− ion. The Ag2–O distances vary from
Fig. 1. Coordination environment of Sm and Ag atoms in 1. All H atoms are omitted for clarity. Symmetry codes: a) 0.5 − x, 0.5 + y, z; b) 0.5 − x, − 0.5 + y, z; c) 0.5 + x, 0.5 − y, -z; d) 1 − x, 0.5 + y, 0.5 − z.
2.479(8)–2.545(11) Å and the Ag2\N3 bond length is 2.226(3) Å. The bond angles of O-Ag2-N fall in the range of 92.1(3)°–160.0(3)°. The 2,7-NDS ligand in 1 only adopts one coordinated mode (μ4) with one of the 7-sulfonate oxygen atoms coordinating to one Ag(I) center and the 2-sulfonate oxygen atoms coordinating to two different Sm(III) ions and one Ag(I) center via a μ3–η1:η2 fashion (Scheme 1a). Each 2,7-NDS ligand leaves three free oxygen atoms. The IN ligand in 1 acts two kinds of coordination fashions: (i) the nitrogen atom coordinates to one Ag(I) center and the carboxylate oxygen atoms link to two Sm(III) ions in a bismonodentate mode (Scheme 1b). (ii) only minor difference between fashion(i) and fashion(ii) is that one of the carboxylate oxygen atoms also coordinates to one Ag(I) center (Scheme 1c). On the basis of such coordination modes of 2,7-NDS and IN ligand, as well as the characteristics of lanthanide metal ions with the affinity for oxygen donors, 1D Sm-based chain with Sm\O\C\O\Sm and Sm\O\S\O\Sm connectivity containing 1D lantern-like four strand helix is built up along the b axis direction, and the distance between neighboring Sm(III) ions in one chain is 4.764 Å (Fig. 2a). Notably, the most important aspect is that this arrangement exactly offers active nitrogen atoms of IN ligands and oxygen atoms of 2,7-NDS ligands to coordinate to adjacent Ag(I) ions to construct 2D 4d–4f elliptical cylinder shaped heterometallic layers along the ac plane (Fig. 2b) [24]. As indicated in Fig. 2b, there are two kinds of bow-like bridges IN–Ag–IN with the angle of N–Ag–N 165.3(3)° and IN–Ag-(2,7-NDS) with the angle of N–Ag–O 92.1(3)° in the upper and lower arc-like layers of 2D heterometallic layers [17a]. Due to carboxylic oxygen atom O11 and sulfonic oxygen atom O2 coordinating to both Sm center and Ag2 center separately with the chelating-bridging mode, the adjacent 2D layers are subtly assembled into a well-organized 3D network coordination framework by [SmAg(μ 2 -O)2 ] units with the Sm–O–Ag angle of 104.210(328)° and 105.327(263)° (Fig. 3). In such a 3D network structure, the ligand 2,7-NDS successfully chelated to lanthanide and transition metal ions and improved the dimensions of the aimed complexes, which is a rare example of covalently bonded 3D 4d–4f heteronuclear networks containing elliptical cylinder shaped layers built by organodisulfonate.
Scheme 1. Coordination modes of 2,7-NDS and IN ligands.
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Fig. 2. (a) View of 1D anionic chain [Ln(2,7-NDS)(IN)3]2− containing a lantern-like four strand helical chain along the b axis direction in compound 1. (b) 2D 4d–4f heteronuclear layer assembled by 1D anionic chain [Ln(2,7-NDS)(IN)3]2− linking the adjacent Ag(I) ions. (c) View of the elliptical cylinder shaped 2D 4d–4f heteronuclear layer.
To better understand the complicated framework, the network topology of compound 1 is analyzed. We define Sm(III) centers as 7connected nodes, IN–Ag–IN and IN–Ag-(2,7-NDS) as bridge linkers. The separations for Sm–Sm are 4.76 Å, 12.234 Å, 12.261 Å and 17.333 Å. Hence, according to the calculation of TOPOS 4.0, the framework of 1 belongs to 7-connected network with the Schläfli symbol of (33;411;56;6) (Fig. 4). Compounds 1–5 were also characterized by powder X-ray diffraction at room temperature in the range of 2θ = 5–50° as shown in Fig. S1. The positions of the diffraction peaks in simulated and experimental patterns correspond well indicating the phase purity of the asprepared products. On account of the similarity of the structures for 1–5, compounds 2, 3 and 4 were selected for thermogravimetric analyses (TGA) to examine the thermal stability of all compounds and their TGA curves are shown
in Fig. S2. The thermogravimetric analyses were done from 30 to 800 °C at a heating rate of 10 °C/min in dry air atmosphere. These frameworks can be stable up to about 350 °C, suggesting relatively high thermal stability of these compounds. Such a thermal stability of 2, 3 and 4 may be attributed to the linkages of IN–Ag–IN and IN–Ag-(2,7-NDS) chains. Then consecutive weight loss from 375 °C is probably caused by the decomposition of the 2,7-NDS and IN ligands, resulting in the collapse of whole 3D frameworks. Because of the excellent luminescent properties of lanthanide complexes, the solid-state photoluminescence of compounds 2 and 4 was measured at room temperature. When excited at 393 nm, the europium compound of 2 emits red fluorescence and exhibits characteristic bands at 579 nm (5 D 0 → 7F 0), 587 and 594 nm (5D0 → 7F1), 613 nm (5D0 → 7F2), 653 nm (5D0 → 7F3), and 704 nm (5D0 → 7F4), arising from the transition of 5D0 → 7FJ (J = 0 → 4) of
Fig. 3. The adjacent elliptical cylinder shaped 2D layers were assembled into 3D coordination frameworks by [SmAg(μ2-O)2] units. (The IN–Ag–IN bridges were omitted for clarity).
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Fig. 4. View of the 3D uninodal 7-connected topological networks of compound 1.
the Eu(III) ions. 5 D 0 → 7 F1 and 5D 0 → 7 F 2 are the most intense transitions(Fig. 5). The 5 D 0 → 7 F1 transition is a magnetic dipole transition, and its intensity is relatively unaffected by the local environment around Eu(III) ions. However, the 5D0 → 7F2 transition is an electric dipole transition, and is hypersensitive to chemical bonds in the vicinity of Eu(III) ions. Furthermore, the intensity of the 5 D 0 → 7 F2 transition decreases as the site symmetry of Eu (III) increases. Therefore, this disparity allows the use of the relative intensities of 5D0 → 7F2 transition and 5D0 → 7F1 transition to probe the symmetry of the Eu(III) centers [25]. For compound 2, the intensity ratio I (5D0 → 7F2)/I (5D0 → 7F1) is ca. 0.76, approximating 0.67, a typical value for a centrosymmetric central Eu(III) ion, which suggests that Eu(III) ions in 2 have a centrosymmetric coordination environment in agreement with the results of the single-crystal X-ray analysis. Compound 4 yields green light when excited at 301 nm, and it gives the characteristic emission of 5 D 4 /7 F J (J = 3 → 6) of the Tb(III) ions (Fig. 6). Two intense emission bands at 544 nm and 593 nm correspond to 5D4 → 7F5 and 5D4 → 7F4 respectively, while the weaker emission bands at 488 nm and 616 nm originate from 5 D4 → 7F6 and 5D4 → 7F3. The direct-current magnetic susceptibility for compounds 3 and 5 was measured in the range of 2 to 300 K under the field of 1000 Oe, as plots of χM vs T and 1/χM vs T as shown in Fig. 7. In the crystal structure of compounds 3 and 5, the 1D Ln-2,7-NDS-Ln chain with ~4.764 Å Ln⋯Ln bond length was separated effectively. Thus the magnetic coupling effects were mainly ascribed to the Ln-cation interactions within the 1D Ln-2,7-NDS-Ln chains. For compound 3, the magnetic
Fig. 5. Solid-state emission spectra of 2 at room temperature (Ex = 393 nm).
Fig. 6. Solid-state emission spectra of 4 at room temperature (Ex = 301 nm).
susceptibility could be simulated by Fisher expressions for infinite chain with SGd = 7/2 [26]. χM ¼
Ng2 β2 SðS þ 1Þ 1 þ u JSðS þ 1Þ kB T − with u ¼ coth : 3kB T 1−u kB T JSðS þ 1Þ
Fig. 7. Plots of χM vs T and 1/χM vs T for compound 3 (a) and 5 (b).
W.-P. Xie et al. / Inorganic Chemistry Communications 40 (2014) 151–156
The best fitting result is g = 2.00, J = − 1.17 × 10−2 cm−1 with 2
∑ðχ calc −χ obs Þ ). Moreover, ∑χ obs 2 the 1/χ M data obey the Curie–Weiss law χ M = C/(T − θ), with C = 8.13 cm 3 K mol − 1 , θ = − 0.19 K. The negative J and θ value indicates the antiferromagnetic coupling between the Gd(III) cations within the 1D Ln-2,7-NDS-Ln chain. However, for compound 5, it is hard to simulate the magnetic data with the isotropic fisher mode due to the strong orbit contributions for Dy(III) cations. But the 1/χ M data of compound 5 also obey the Curie–Weiss law with C = 14.17 cm3 K mol− 1 and θ = − 3.38 K. The negative θ value may also indicate the antiferromagnetic coupling in the 1D Dy-2,7-NDS-Dy chain. In conclusion, five novel 3D 4d–4f heterometallic coordination polymers have been synthesized through hydrothermal reactions by using 2,7-naphthalenedisulfonate as the main ligand and isonicotinic acid as the co-ligand. These isostructural 3D coordination frameworks were built up by 2D elliptical cylinder shaped [LnAg2(2,7-NDS)(IN)3] layers which are constructed by 1D anionic chains [Ln(2,7-NDS)(IN)3]2 − linking the adjacent Ag(I) ions, and [LnAg(μ2-O)2] units possessing a 7-connected topology with the Schläfli symbol of {33;411;56;6}. This work may enrich the family of coordination chemistry of the arenedisulfonate ligands. In addition, Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence and complexes 3 and 5 show antiferromagnetic behaviours. agreement factor R = 2.58 × 10−5 (R=
Acknowledgments This work was financially supported by the National Nature Science Foundation of China (20971047, U0734005 and 21271076), Key Program of Guangdong Universities Science and Technology innovation (cxzd1020), and Planning Program of Guangzhou City Science and Technology (2013J4100049).
[6]
[7]
[8]
[9]
[10]
[11]
Appendix A. Supplementary material CCDC 926932–926934, 926937–926938 contain the supplementary crystallographic data for 1–5. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif, or from the Cambridge Crystallographic Data Centre, 12 Union Road, CambridgeCB2 1EZ, UK[Fax:+44(1223)336033; E-mail: [email protected]]. Supplementary data to this article can be found online at http://dx.doi.org/10.1016/j.inoche.2013.11. 029.
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(c) X.F. Li, R. Cao, Syntheses, structure and properties of three-dimensional pillared-layer Ag(I)–Ln(III) heterometallic coordination polymers based on mixed isonicotinate and hemimellitate ligands, J. Solid State Chem. 196 (2012) 182–186. [18] Synthesis of compounds 1–5: a mixture of 2,7-naphthalenedisulfonate sodium salt (0.1661 g, 0.5 mmol), isonicotinic acid (0.127 g, 1.0 mmol), Sm(NO3)·6H2O for 1 (0.1333 g, 0.3 mmol), Eu(NO3)·6H2O for 2 (0.1338 g, 0.3 mmol), Gd(NO3)·6H2O for 3 (0.1353 g, 0.3 mmol), Tb(NO3)·6H2O for 4 (0.1359 g, 0.3 mmol), Dy(NO3)·6H2O for 5 (0.1369 g, 0.3 mmol), AgNO3 (0.0510 g, 0.3 mmol) were dissolved in 8 mL of H2O, then heated to 180 °C for 72 h in a 23 mL Teflon-lined stainless-steel autoclave. After cooling to room temperature at a rate of 5 °C/h, yellow block crystals were collected manually, washed with distilled water for several times and dried in air. For 1, Yield 45% based on Sm. Anal. Calcd for C28H18Ag2N3O12S2Sm: C 32.98, H 1.77, N 4.13%. Found: C 32.97, H 1.76, N 4.11%. IR data (KBr, cm−1): 3469(s), 3195 (s), 1604(s), 1548(m), 1406(s), 1388(s), 1240(m), 1170(m), 1096(m), 1021(m), 853(w), 777(m), 691(m), 569(m). For 2, Yield 44% based on Eu Anal. Calcd for C28H18Ag2N3O12S2Eu: C 32.93, H 1.76, N 4.13%. Found: C 32.92, H 1.75, N 4.12%. IR data (KBr, cm−1): 3443(s), 3202(s), 1606(s), 1548(m), 1406(s), 1382(s), 1240(m), 1169(m), 1095(m), 1020(m), 855(w), 775(m), 690(m), 567(m). For 3, Yield 42% based on Gd. Anal. Calcd for C28H18Ag2N3O12S2Gd: C 32.76, H 1.76, N 4.10%. Found: C 32.75, H 1.76, N 4.09%. IR data (KBr, cm−1): 3445(s), 3203(s), 1607(s), 1549(m), 1406(s), 1383(s), 1230(m), 1170(m), 1096(m), 1021(m), 849(w), 776(w), 691(m), 567(m). For 4, Yield 41% based on Tb. Anal. Calcd for C28H18Ag2N3O12S2Tb: C 32.71, H 1.75, N 4.09%. Found: C 32.70, H 1.74, N 4.08%. IR data (KBr, cm−1): 3463(s), 3199(s), 1607(s), 1549(m), 1407(s), 1385(s), 1228(m), 1171(m), 1096(m), 1022(m), 851(w), 777(m), 690(m), 568(m). For 5, Yield 40% based on Dy. Anal. Calcd for C28H18Ag2N3O12S2Dy: C 32.60, H 1.75, N 4.07%. Found: C 32.59, H 1.76, N 4.05%. FT-IR (KBr, cm−1): 3435(s), 3200(s), 1608(s), 1551(m), 1406(s), 1384(s), 1229(m), 1173(m), 1097(m), 1022(m), 849(w), 776(m), 691(m), 566 (m). [19] L.J. Bellamy, The infrared spectra of complex molecules, Wiley, New York, 1958. 258. [20] Q.Y. Liu, W.F. Wang, J.K. Tang, Diversity of lanthanide(III)–organic extended frameworks with a 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid ligand: syntheses, structures, and magnetic and luminescent properties, Inorg. Chem. 51 (2012) 2381–2392.
[21] Crystal data for 1: Orthorhombic, Pbca, a = 17.8453(18) Å, b = 9.5012(10) Å, c = 34.507(4) Å, α = 90° β = 90° γ = 90° V = 5850.7(11) Å3, Z = 8, Dc = 2.313, F(000) = 3928.0, GOF = 1.069, R1(I N 2σ(I)) = 0.0547, wR2 (all data) = 0.1622. 2: Orthorhombic, Pbca, a = 17.847(2) Å, b = 9.4180(12) Å, c = 34.602(4) Å, α = 90° β = 90° γ = 90° V = 5816.0(12) Å3, Z = 8, Dc = 2.330, F(000) = 3936.0, GOF = 1.142, R1(I N 2σ(I)) = 0.0431, wR2 (all data) = 0.1016. 3: Orthorhombic, Pbca, a = 17.928(3) Å, b = 9.4592(14) Å, c = 34.521(5) Å, α = 90 ° β = 90° γ = 90° V = 5854.1(15) Å3, Z = 8, Dc = 2.327, F(000) = 3944.0, GOF = 1.099, R1(I N 2σ(I)) = 0.0601, wR2 (all data) = 0.1720. 4: Orthorhombic, Pbca, a = 17.9026(19) Å, b = 9.4035(10) Å, c = 34.477(4)Å, α = 90° β = 90° γ = 90° V = 5804.1(11) Å3, Z = 8, Dc = 2.351, F(000) = 3952.0, GOF = 1.062, R1(I N 2σ(I)) = 0.0517, wR2 (all data) = 0.1529. 5: Orthorhombic, Pbca, a = 17.906(2) Å, b = 9.4075(11) Å, c = 34.360(4) Å, α = 90 ° β = 90° γ = 90 ° V = 5788.0(12) Å3, Z = 8, Dc = 2.366, F(000) = 3960.0, GOF = 1.057, R1(I N 2σ(I)) = 0.0580, wR2 (all data) = 0.1689. [22] J.X. Liu, Y.F. Hu, T. Zhu, Coordination complexes based on pentacyclohexanocucurbit [5] uril and lanthanide(III) ions: lanthanide contraction effect induced structural variation, CrystEngComm 14 (2012) 6983–6989. [23] (a) C.H. Chen, J.W. Cai, X.M. Chen, Synthesis and crystal structures of four nickel(II) 1,5-naphthalenedisulfonate compounds, J. Chem. Crystallogr. 31 (2001) 271–280; (b) J.W. Cai, M.L. Lin, Selective amine intercalation behavior of [Cd(1,5-nds)(H2O)2, J. Mater. Chem. 13 (2003) 1806–1811. [24] L. Liang, G. Peng, H. Deng, A new family of 3d–4f heterometallic tetrazole-based coordination frameworks: in situ tetrazole ligand synthesis, structure, luminescence, and magnetic properties, Cryst. Growth Des. 12 (2012) 1151–1158. [25] (a) C. Serre, C. Thouvenot, Synthesis, characterisation and luminescent properties of a new three-dimensional lanthanide trimesate: M((C6H3)–(CO2)3) (M = Y, Ln) or MIL-78, J. Mater. Chem. 14 (2004) 1540–1543; (b) M.D. Allendorf, C.A. Bauer, Luminescent metal–organic frameworks, Chem. Soc. Rev. 38 (2009) 1330–1352. [26] M.E. Fisher, Magnetism in one-dimensional systems—the Heisenberg Model for infinite spin, Am. J. Phys. 32 (1964) 343.