Luminescent Lanthanide(III) Carboxylate−Phosphonates with Helical

CRYSTAL GROWTH & DESIGN

Luminescent Lanthanide(III) Carboxylate-Phosphonates with Helical Tunnels Si-Fu Tang, Jun-Ling Song, Xiu-Ling Li, and Jiang-Gao Mao* State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou 350002, P. R. China

2006 VOL. 6, NO. 10 2322-2326

ReceiVed April 27, 2006; ReVised Manuscript ReceiVed July 21, 2006

ABSTRACT: Hydrothermal reactions of lanthanide(III) salts with H4PMIDA (N-(phosphonomethyl)iminodiacetic acid) led to seven new isostructural lanthanide(III) carboxylate phosphonates, namely, Ln(HPMIDA)(H2O)2‚H2O (Ln ) Gd, 1; Tb, 2; Dy, 3; Y, 4; Er, 5; Yb, 6; Lu, 7). Their structures feature a novel 3D framework. The lanthanide(III) ion is eight-coordinated by a chelating HPMIDA in a tetradentate fashion (1 N and 3 O), one carboxylate oxygen and one phosphonate oxygen from two other HPMIDA anions, and two aqua ligands. The HPMIDA anion is hexadentate. It chelates with a Ln(III) ion tetradentatedly and also bridges with two other Ln(III) ions. The phosphonate group is singly protonated. One of the carboxylic groups is unidentate, whereas the other is bidentate bridging. Compound 2 exhibits very strong characteristic emission bands for the terbium(III) ion in the visible region under 380 nm excitation, with the Tb (5D0) lifetime for λex,em ) 380 and 488 nm being about 1 ms. Compounds 1 and 5 display very broad ligand-centered emission bands in the blue light region. Introduction The chemistry of metal phosphonates has been expending rapidly in the past two decades because of their potential applications in the areas of catalysis, ion exchange, proton conductivity, intercalation chemistry, photochemistry, and materials chemistry.1 Most of metal phosphonates exhibit a variety of open framework architectures such as layered and microporous structures. An effective method for preparing new materials with microporous or open framework structures is the use of bifunctional or multifunctional anionic units, such as diphosphonates, aminophosphonates, or phosphonocarboxylates.2-5 Lanthanide phosphonates may exhibit useful luminescence properties in both visible and near-IR regions; therefore, the elucidation of the structures of lanthanide phosphonates becomes very important.6 Up until now, reports on lanthanide phosphonates have still been limited and a number of them are based on X-ray powder diffraction.7-15 Lanthanide phosphonates have low solubility in most solvents and are normally of poor crystallinity. Hence, it is rendered difficult to obtain single crystals suitable for their structural studies. Results from our group indicate that introducing a second ligand such as 5-sulfoisophthalic acid (H3BTS) or oxalic acid, whose lanthanide compounds have good solubility and very good crystallinity, into the lanthanide-phosphonate system can lead to novel luminescent lanthanide phosphonate hybrids.15 Another alternative is the introduction of functional groups such as crown ether,8a,13 hydroxy,14 amino,16 pyridyl,17 and carboxylate.18 Among these functional groups, carboxylate group or amino acid are very important. So far, a number of 2D or 3D lanthanide carboxylate phosphonates have been prepared.18 N-(Phosphonomethyl)iminodiacetic acid (H4PMIDA) contains an aminodiacetatic acid moiety (N(CH2COOH)2) and is a versatile ligand that can adopt a variety of coordination modes when reacting with transition-metal salts.19 We deem that such a ligand should be also able to form a variety of lanthanide(III) complexes, although so far none have been reported. Hydrothermal reactions of H4PMIDA with lanthanide(III) salts afforded seven novel lanthanide(III) carboxylate-phosphonates, namely, Ln(HPMIDA)(H2O)2‚H2O (Ln ) Gd, 1; Tb, 2; Dy, 3; Y, 4; Er, 5; Yb, 6; Lu, * Corresponding author. E-mail: [email protected].

7). Their structures feature a three-dimensional network with helical tunnels. Herein, we report their syntheses, crystal structures, and luminescence properties. Experimental Section Materials and Instrumentation. (HOOCCH2)2NCH2PO3H2 (H4PMIDA) was prepared by a Mannich type reaction according to procedures described previously.20 All other chemicals were obtained from commercial sources and used without further purification. Elemental analyses were performed on a Vario EL III elemental analyzer. Thermogravimetric analyses were carried out on a NETZSCH STA 449C unit at a heating rate of 10 °C/min under a nitrogen atmosphere. IR spectra were recorded on a Magna 750 FT-IR spectrometer photometer as KBr pellets in the 4000-400 cm-1. Photoluminescence analyses were performed on an Edinburgh FLS920 fluorescence spectrometer. NLO properties were performed on a homemade instrument using an Nd:YAG laser as the light source. Preparation of Ln(HPMIDA)(H2O)2‚H2O (Ln ) Gd, 1; Tb, 2; Dy, 3; Y, 4; Er, 5; Yb, 6; Lu, 7). A mixture of lanthanide salt (lanthanide chloride for 1, 6, and 7; lanthanide nitrate for 2; lanthanide hydroxide for 3-5) (1.0 mmol) and H4PMIDA (1.0 mmol) in 10 mL of distilled water was sealed into a bomb equipped with a Teflon liner (25 mL) and then heated at 150 °C (165 °C for 3-5) for 3 days. Compounds 1-7 were obtained in a yield of 20, 70, 65, 60, 82, 58, and 55%, respectively (based on lanthanide metal). Elemental anal. Calcd for C5H13NO10PGd: C, 13.79; H, 3.01; N, 3.22. Found: C, 13.80; H, 3.09; N, 3.19. IR (KBr, cm-1): 3584 m, 3417 m, 3182 m, 1574 vs, 1457 m, 1403 s, 1345 w, 1327 w, 1261 m, 1169 s, 1146 m, 1064 m, 1006 w, 979 w, 946 m, 912 m, 859 w, 782 w. Elemental anal. Calcd for C5H13NO10PTb: C, 13.74; H, 3.00; N, 3.21. Found: C, 13.79; H, 3.12; N, 3.19. IR (KBr, cm-1): 3588 m, 3419 m, 3217 m, 1573 vs, 1458 m, 1422 s, 1406 s, 1344 m, 1326 m, 1309 m, 1261 m, 1170 s, 1146 m, 1064 m, 1006 m, 980 w, 946 m, 912 m, 859 w, 782 w. Elemental anal. Calcd for C5H13NO10PDy: C, 13.63; H, 2.97; N, 3.18. Found: C, 13.69; H, 2.82; N, 3.12. IR (KBr, cm-1): 3584 m, 3418 m, 3221 m, 1575 vs, 1458 m, 1441 s, 1423 s, 1407 s, 1344 m, 1326 w, 1262 m, 1171 s, 1146 m, 1066 m, 1006 m, 980 w, 946 m, 912 m, 860 w, 783 w. Elemental anal. Calcd for C5H13NO10PY: C, 16.36; H, 3.57; N, 3.82. Found: C, 16.31; H, 3.62; N, 3.88. IR (KBr, cm-1): 3589 m, 3420 m, 3224 m, 1578 vs, 1459 m, 1442 s, 1423 s, 1406 s, 1344 m, 1326 w, 1261 m, 1173 s, 1149 m, 1068 m, 1006 m, 980 w, 946 m, 913 m, 859 w, 783 w. Elemental anal. Calcd for C5H13NO10PEr: C, 13.48; H, 2.94; N, 3.15. Found: C, 13.61; H, 2.96; N, 3.09. IR (KBr, cm-1): 3588 m, 3422 m, 3225 m, 1577 vs, 1459 m, 1442 s, 1423 s, 1407 s, 1344 m, 1326 w, 1261 m, 1173 s, 1149 m, 1066 m, 980 w, 946 m, 913 m, 860 w, 783 w. Elemental anal. Calcd for C5H13NO10PYb: C, 13.31; H, 2.90; N, 3.11. Found: C, 13.37; H, 2.96; N, 3.20. IR (KBr, cm-1):

10.1021/cg060248l CCC: $33.50 © 2006 American Chemical Society Published on Web 08/29/2006

Ln(III) Carboxylate-Phosphonates with Helical Tunnels

Crystal Growth & Design, Vol. 6, No. 10, 2006 2323

Table 1. Crystal Data and Structure Refinements for Compounds 1-7

formula fw space group a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg) V (Å3) Z Dcalcd (g cm-3) µ (mm-1) GOF on F2 R1, wR2 (I > 2σ(I))a R1, wR2 (all data) a

1

2

3

4

5

6

7

C5H13NO10PGd 435.38 P212121 9.10(1) 8.915(2) 15.874(2) 90 90 90 1288.4(3) 4 2.2454 5.336

C5H13NO10PTb 437.06 P212121 9.06(1) 8.913(2) 15.781(2) 90 90 90 1274.49(3) 4 2.2786 5.679

C5H13NO10PDy 440.63 P212121 9.01(4) 8.89(5) 15.8(2) 90 90 90 1262.4(1) 4 2.3192 5.991

C5H13NO10PY 367.04 P212121 9.0223(7) 8.9108(8) 15.684(1) 90 90 90 1260.9(2) 4 1.934 4.797 0.996 0.0356, 0.0670 0.0452, 0.0706

C5H13NO10PEr 445.39 P212121 9.009(2) 9.009(2) 15.799(4) 90 90 90 1282.1(4) 4 2.307 6.714 1.122 0.0231, 0.0542 0.0242, 0.0547

C5H13NO10PYb 451.17 P212121 8.981(2) 8.981(2) 15.65(4) 90 90 90 1258.7(5) 4 2.3816 7.457

C5H13NO10PLu 453.10 P212121 8.9466(1) 8.9062(2) 15.5353(3) 90 90 90 1237.86(4) 4 2.431 8.150 1.133 0.0214, 0.0494 0.0223, 0.0499

R1 ) ∑||Fo| - |Fc||/∑|Fo|, wR2 ) {∑w[(Fo)2 - (Fc)2]2/∑w[(Fo)2]2}1/2.

Table 2. Selected Bond Lengths (Å) for Compounds 4, 5, and 7a

Ln(1)-O(12)#1 Ln(1)-O(13) Ln(1)-O(1) Ln(1)-O(2)#2 Ln(1)-O(4) Ln(1)-O(1W) Ln(1)-O(2W) Ln(1)-N(1) O(11)‚‚‚O(3)#3 O(1W)‚‚‚O(3W)

4 (Y)

5 (Er)

7 (Lu)

2.251(3) 2.275(3) 2.315(3) 2.337(3) 2.369(3) 2.384(4) 2.425(3) 2.667(3) 2.508(5) 2.721(7)

2.268(3) 2.304(3) 2.314(4) 2.348(3) 2.377(4) 2.385(4) 2.409(3) 2.659(4) 2.545(6) 2.744(8)

2.222(4) 2.239(4) 2.278(4) 2.309(4) 2.332(5) 2.345(4) 2.391(4) 2.629(5) 2.501(7) 2.744(9)

a Symmetry transformations used to generate equivalent atoms: #1 -x, y - 1/2, -z + 3/2; #2 x + 1/2, -y + 3/2, -z + 1; #3 x, y + 1, z.

3592 m, 3415 m, 3230 m, 1581 vs, 1460 m, 1443 s, 1423 s, 1407 s, 1344 m, 1325 m, 1261 m, 1175 s, 1151 m, 1068 m, 1007 m, 980 w, 946 s, 914 m, 860 w, 784 m. Elemental anal. Calcd for C5H13NO10PLu: C, 13.26; H, 2.89; N, 3.09. Found: C, 13.18; H, 2.87; N, 3.10. IR (KBr, cm-1): 3586 m, 3424 m, 3320 s, 3231 s, 1582 vs, 1461 m, 1443 s, 1424 s, 1408 s, 1344 m, 1325 w, 1261 m, 1176 s, 1152 m, 1068 m, 1007 m, 981 w, 947 s, 914 m, 860 w, 785 m. Based on X-ray powder diffraction studies, compounds 1-7 are prepared as pure phases. The measured patterns are in good agreement with those simulated from single-crystal structures (see the Supporting Information). Single-Crystal Structure Determination. Data collections for compounds 1-7 were performed on a Siemens Smart CCD diffractometer or Rigaku Mercury CCD equipped with a graphite-monochromated MoKR radiation (λ ) 0.71073 Å). Cell parameter measurements indicate that all seven compounds are isostructural, hence full data collections were performed for only compounds 4, 5, and 7. Intensity data were collected by the narrow frame method at 293 K. The data sets were corrected for Lorentz and polarization factors as well as for absorption by the SADABS program or Multiscan method.21 All structures were solved by the direct methods and refined by full-matrix least-squares fitting on F2 by SHELX-97.21 All non-hydrogen atoms were refined with anisotropic thermal parameters. Hydrogen atoms except those for water molecules were located at geometrically calculated positions and refined with isotropic thermal parameters. Hydrogen atoms for water molecules in compounds 4, 5, and 7 were not included in the refinements. Crystallographic data and structural refinements for compounds 1-7 are summarized in Table 1. Selected bond lengths for compounds 4, 5, and 7 are listed in Table 2. More details on the crystallographic studies as well as atom displacement parameters are given as the Supporting Information.

Results and Discussion Hydrothermal reactions of H4PMIDA with lanthanide(III) salts afforded seven novel lanthanide(III) carboxylate-phos-

Figure 1. ORTEP representation of a selected unit of compound 5. The thermal ellipsoids are drawn at the 50% probability level. Symmetry codes for the generated atoms: (a) -x, -1/2 + y, 3/2 - z; (b) 1/2 + x, 3 /2 - y, 1 - z; (c) -1/2 + x, 3/2 - y, 1 - z; (d) -x, 1/2 + y, 3/2 - z.

phonates, namely, Ln(HPMIDA)(H2O)2‚H2O (Ln ) Gd, 1; Tb, 2; Dy, 3; Y, 4; Er, 5; Yb, 6; Lu, 7). Their structures feature a three-dimensional network with helical tunnels. Reports on chiral lanthanide phosphonates are still very rare.8a,22 Compounds 1-7 are isostructural, hence only the structure of 5 will be discussed in detail as a representation. The asymmetric unit of 5 consists of one unique erbium(III) ion, a HPMIDA anion, two aqua ligands, and a lattice water molecule (Figure 1). The erbium(III) ion is eight-coordinated by a chelating HPMIDA in a tetradentate fashion (1 N and 3 O), one carboxylate oxygen and one phosphonate oxygen from two other HPMIDA anions, and two aqua ligands. Its coordination geometry can be viewed as being a distorted bicapped trigonal prism in which N(1) and O(2W) act as two capping atoms. The Er-O distances are in the range 2.268(3)-2.409(3) Å, which are comparable to those reported for other Er(III) phosphonates.15b,17a,18b The Er-N distance is 2.659(4) Å. The HPMIDA anion acts as a hexadentate metal linker. It chelates with an erbium(III) ion in a tetradentate fashion (1N and 3O) and bridges to two other erbium ions. One carboxylic group is unidentate, whereas the other is bidentate bridging. The phosphonate group is singly protonated. On the basis of P-O distances, O(11) is protonated. The Er(HPMIDA) chelating units are interconnected via bridging carboxylate and phosphonate groups into a 3D network with helical tunnels along the a-axis (Figure 2). The tunnel is formed by 10-membered rings composed of six Er(III) ions and four phosphonate groups. The size of the tunnel is about 5.6 × 12.9 Å on the basis of structure data. The lattice water molecules

2324 Crystal Growth & Design, Vol. 6, No. 10, 2006

Tang et al.

Figure 2. View of the structure of compound 5 down the a-axis. The phosphonate tetrahedra are shaded in purple. Er, C, N, and O atoms are drawn as green, black, blue, and red circles, respectively. Hydrogen bonds are drawn as dashed lines.

are located at the tunnels and form strong hydrogen bonds with aqua ligands (O(1w)‚‚‚O(3w) 2.744(8) Å). Hydrogen bonds are also formed between the noncoordination carboxylate oxygen atoms (O(3)) and noncoordination phosphonate group oxygen atoms (O(11), symmetry code: x, y - 1, z) with O‚‚‚O separations of 2.545(6) Å (Figure 2, Table 2). The solventaccessible volumes in compounds 4, 5, and 7 are 15.7, 15.6, and 15.9%, respectively, according to calculations using the PLATON program.23 A better insight into the nature of the involved framework can be achieved by the application of a topological approach. Despite the existence of the aqua ligands, each erbium atom is linked by three HPMIDA ligands and each HPMIDA ligand bridges to three erbium atoms; therefore, the erbium centers and HPMIDA ligands can be regarded as being three-connected building units and the whole network can thus be represented topologically by two types of three-coordinate nodes (triangularpyramidal and trigonal-planar nodes, respectively). The whole structure can be extended to an unusual non-interpenetrated (10, 3)-d net, as displayed in Figure 3. The extended Schla¨fli symbol of this net is 102.104.104, which is called the utp net.24 An interesting feature of this (10, 3) net is the presence of parallel single helices running through the structure, as highlighted in purple and yellow lines in Figure 3. This net is constructed by tetragonal right-handed and octagonal left-handed helices along the b-axis. Each tetragonal helix connects with four adjacent octagonal helices, whereas each octagonal helix connects with four tetragonal and four octagonal helices by sharing a common edge. Because the right- and left-handed helices are alternatively arranged, the whole net is therefore racemic. To the best of our knowledge, there are currently only four known examples with this utp type assigned in the papers, and only one of them has a non-interpenetrated utp net.24 The TGA curves of the title compounds are similar, and compound 5 was used as an example (Figure 4). It exhibits three main steps of weight loss. The weight loss from 70 to 265 °C corresponds to the release of three water molecules per formula unit. The observed weight loss of 12.3% is close to the calculated value (12.1%). The second step covers a temperature range of 265-600 °C, during which the carboxylate phosphonate ligand is combusted. The total weight loss at 995 °C is about 33.1%, and the final products are not identified. However, we suspect they are mainly ErPO4. The much larger total weight loss for compound 4 (40.1%) is due to its having a much smaller formula weight than the other compounds. The weight of

Figure 3. Schematic representation of the (10, 3) net in 5 along the b-axis. Highlighted are right-handed (purple) and left-handed (yellow) helices.

Figure 4. TGA curves for compounds 1-7.

materials released or combusted during the decomposition is expected to be about the same for all seven compounds. The solid-state luminescence properties of compounds 1, 2, and 5 were investigated at room temperature. The emission spectra are given in Figure 5. Compound 1 exhibits only a broad blue fluorescence emission band at λmax ) 406 nm (λex ) 325 nm) (Figure 5a), which corresponds to a ligand-centered (LC) fluorescence. The metal-centered (MC) electronic levels of the Gd3+ ion are known to be located at 31 000 cm-1, which is typically well above the ligand-centered electronic levels of the organic ligands. Therefore, ligand-to-metal energy transfer and the consequent MC luminescence cannot be observed.25 Compound 2 exhibits four very strong characteristic emission bands for the terbium(III) ion in the visible region under excitation at 380 nm (Figure 5b). These emission bands are 489.5 nm (5D4 f7F6), 546.5 nm (5D4f7F5), 582.0 (5D4 f7F4), and 621.5 nm (5D4 f7F3). The Tb (5D0) lifetime of 2 for λex,em ) 380, 488 nm is about 1 ms. Under excitation of 346 nm, compound 5 displays a broad blue fluorescence emission band at λmax ) 419 nm (Figure 5a), which corresponds to a ligand-centered (LC)

Ln(III) Carboxylate-Phosphonates with Helical Tunnels

Crystal Growth & Design, Vol. 6, No. 10, 2006 2325

Acknowledgment. This work was supported by the National Natural Science Foundation of China (20371047, 20573113, and 20521101) and NSF of Fujian Province (E0420003). Supporting Information Available: X-ray crystallographic files in CIF format for the structure determination of compounds 4, 5, and 7, as well as the XRD powder patterns for all seven compounds. This material is available free of charge via the Internet at http:// pubs.acs.org.

References

Figure 5. (a) Solid-state emission spectra of 1 (black curves) and compound 5 (red curves) at room temperature; (b) room-temperature solid-state emission spectrum of compound 2.

fluorescence. No emission band in near-IR region was found, probably because of the quenching effect of the luminescence state by high-frequency vibrating water molecules.15a All of the above seven compounds crystallize in the noncentrosymmetric space group P212121; hence, they may possess the NLO properties. The results of our measurements indicated that their SHG signals were very weak, which confirms that these compounds are racemic. Conclusion By using the phosphonic acid containing an aminodiacetic acid moiety, H4PMIDA, as a metal linker, we have synthesized seven lanthanide carboxylate-phosphonates with a general formula Ln(HPMIDA)(H2O)2‚H2O (Ln ) Gd, Tb, Dy, Y, Er, Yb, Lu). Their structures feature a novel 3D structure with helical channels. Topologically, the whole structure can be viewed as being an unusual non-interpenetrated utp net. Compounds 1 and 5 displayed very broad intraligand emission bands in the blue light region, whereas compound 2 exhibited strong luminescence in the green light region. The results of our study indicate that by using a phosphonic acid attached to an amino acid moiety, we can obtain lanthanide phosphonates with good crystallinity and novel structures as well as strong luminescence.

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