Inorganic Chemistry Communications 7 (2004) 611613 www.elsevier.

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Syntheses, structures and luminescent properties of four new 1D lanthanide complexes with 2-thiopheneacetic acid ligandq
Li-Zhen Cai, Wen-Tong Chen, Ming-Sheng Wang, Guo-Cong Guo *, Jin-Shun Huang
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Xihe, Fuzhou, Fujian 350002, PR China Received 12 December 2003; accepted 15 February 2004 Available online 19 March 2004

Abstract Four complexes, Ln2 (C6 H5 SO2 )6 (H2 O)3 2.25H2 O (C6 H5 SO2 2-thiopheneacetic acid, Ln Ce (1), Pr (2), Nd (3), Sm (4)), have been synthesized with hydrothermal route. The X-ray diraction analyses reveal that they are characterized by the 1D structure and uorescence studies show they display interesting luminescent properties in solid state. 2004 Elsevier B.V. All rights reserved.
Keywords: Crystal structure; Luminescence; Lanthanide; 2-thiopheneacetic acid

In the past few years, lanthanide compounds have attached extremely interesting because they not only posses potential properties in luminescent and magnetic, but also generate diversities of structures by selecting dierent bridging ligands [1]. A lot of work have been done to design and synthesize lanthanide chelates with good luminescent properties [25]. Chelating agents commonly used for these compounds include b-diketonates, [4,6] pyridinecarboxylic acids, [2,5,7] benzene carboxylic acid [3] and other heteroaromatics [8]. In view of the high luminescence quantum yields of the europium salt of 4-(thin-2-yl)pyriq *

dine-2,6-dicarboxylic acid [8], we select 2-thiopheneacetic acid as bridging ligand-to-investigate the inuence on the lanthanide luminescence by ligand to metal energy transfer mechanism. We report herein the syntheses and structures of four new lanthanide complexes with 2-thiopheneacetic acid using hydrothermal technique, to the best of our knowledge, the metal complexes that involve 2-thiopheneacetic acid as the bridging ligand have not yet been experimentally or theoretically described so far. The prismatic crystals of compounds 14, Ln2 (C6 H5 SO2 )6 (H2 O)3 2.25H2 O 1, were synthesized by

Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2004.02.015. Corresponding author. Tel.: +86-591-3705882; fax: +86-591-3714946. E-mail address: gcguo@ms.fjirsm.ac.cn (G.-C. Guo). 1 1 mmol of 2-thiopheneacetic acid was dissolved in 10 ml of H2 O, then Me4 NOH was added dropwise to the above solution until pH was 78, nally, 0.5 mmol of salt of lanthanide (Ce(NO3 )3 6H2 O for 1, LnCl3 6H2 O for 24) was added. The reaction mixtures were heated at 170 C in a Teon-lined stainless steel autoclave for 5 days. The ltrates were left to stand in atmosphere for several days then crystals suitable for X-ray determination were formed. Anal. 1: Calcd. (%): C, 35.39; H, 3.32; O, 22.59; S, 15.74. Found: C, 35.43; H, 3.35; O, 22.62; S, 15.77. 2: Calcd. (%): C, 35.35; H, 3.31; O, 22.56; S, 15.72. Found: C, 35.34; H, 3.33; O, 22.50; S, 15.76. 3: Calcd. (%): C, 35.15; H, 3.29; O, 22.44; S, 15.64. Found: C, 35.17; H, 3.33; O, 22.49; S, 15.67. 4: Calcd. (%): C, 34.81; H, 3.26; O, 22.22; S, 15.48. Found: C, 34.84; H, 3.29; O, 22.24; S, 15.51. IR (cm1 , KBr): 1: mas (COO): 1542.79, ms (COO): 1384.661488.80; 2: mas (COO): 1542.79, ms (COO): 1384.661488.80; 3: mas (COO): 1546.65, ms (COO): 1390.441488.80; 4: mas (COO): 1548.58, ms (COO): 1388.511488.80.1 mmol of 2-thiopheneacetic acid was dissolved in 10 ml of H2 O, then Me4 NOH was added dropwise to the above solution until pH was 78, nally, 0.5 mmol of salt of lanthanide (Ce(NO3 )3 6H2 O for 1, LnCl3 6H2 O for 24) was added. The reaction mixtures were heated at 170 C in a Teon-lined stainless steel autoclave for 5 days. The ltrates were left to stand in atmosphere for several days then crystals suitable for X-ray determination were formed. Anal. 1: Calcd. (%): C, 35.39; H, 3.32; O, 22.59; S, 15.74. Found: C, 35.43; H, 3.35; O, 22.62; S, 15.77. 2: Calcd. (%): C, 35.35; H, 3.31; O, 22.56; S, 15.72. Found: C, 35.34; H, 3.33; O, 22.50; S, 15.76. 3: Calcd. (%): C, 35.15; H, 3.29; O, 22.44; S, 15.64. Found: C, 35.17; H, 3.33; O, 22.49; S, 15.67. 4: Calcd. (%): C, 34.81; H, 3.26; O, 22.22; S, 15.48. Found: C, 34.84; H, 3.29; O, 22.24; S, 15.51. IR (cm1 , KBr): 1: mas (COO): 1542.79, ms (COO): 1384.661488.80; 2: mas (COO): 1542.79, ms (COO): 1384.661488.80; 3: mas (COO): 1546.65, ms (COO): 1390.441488.80; 4: mas (COO): 1548.58, ms (COO): 1388.511488.80. 1387-7003/$ - see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2004.02.015

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L.-Z. Cai et al. / Inorganic Chemistry Communications 7 (2004) 611613

the reaction of 2-thiopheneacetic acid, salt of trivalent lanthanide, Me4 NOH and H2 O under hydrothermal conditions. The compounds are very stable in air at ambient temperature. Single crystal X-ray analysis 2 of present complexes reveals that they are isomorphous and compound 1 is discussed in detail. Each structure of the complexes consists of two crystallographically independent Ln (III) ions (Ln1 and Ln2), six crystallographically independent 2-thiopheneacetic acid ligands, three coordinated water molecules, and packing water molecules, as shown in Fig. 1. The Ln1 ion is decacoordinated with two water molecules and eight oxygen atoms from six 2-thiopheneacetic acid ligands. While the Ln2 ion is nine-coordinated, consisting of a water molecule and eight oxygen atoms from the carboxylate groups of six 2-thiopheneacetic acid ligands. The geometry of the Ln2 center can be related to a tricapped trigonal prism with the two outer triangular faces formed by atoms O21, O52, O3W and O32, O12, O42, and the three capping positions occupied by atoms O51, O61, and O11. It is noted that one of the LnO bond distances (Ce1O42 2.891(5), Pr1O41 2.924(5),  Nd1O42 2.901(6), Sm1O21 2.840(4) A) in 14 is obviously longer than those in lanthanide compounds bridged by carboxylate group [2], [11] and can be regarded as a weak interaction [12]. The rest of LnO  bond distances ranging from 2.363(4) to 2.762(5) A in the present compounds are normal as compared with lanthanide carboxylates. The Ln1 and Ln2 atoms in 14 are triply bridged by three 2-thiopheneacetic acid ligands to form an innite chain extending along the [1 0 0] direction with alternate intra-chain Ln Ln distances (Ln Ln 4.2738(4)   and 4.3118(4) A for 1, 4.2523(5) and 4.2971(5) A for 2,  4.2738(4) and 4.3119(4) A for 3, 4.1978(3) and 4.2454(3)  A for 4). The six crystallographically independent 2Crystal data: 1: crystal dimensions 0.36 0.14 0.08 mm , Fw 1221:78, orthorhombic, space group Aba2, a 16:070,  b 19:92934, c 29:99537, V 9606:53 A3 , Z 8, Dc 1:690 mg/m3 , F 0 0 0 4852, R 0:0633. 2: crystal dimensions 0.26 0.20 0.06 mm3 , Fw 1223:36, orthorhombic, space group   Aba2, a 15:9981, b 19:8831, c 29:9622 A, V 95301 A3 , Z 8, Dc 1:705 mg/m3 , F 0 0 0 4868, R 0:0739. 3: crystal dimensions 0.56 0.14 0.14 mm3 , Fw 1230:02, orthorhombic,  space group Aba2, a 16:0701, b 19:92934, c 29:99537 A,  V 9606:53 A3 , Z 8, Dc 1:701 mg/m3 , F 0 0 0 4884, R 0:0632. 4: crystal dimensions 0.36 0.16 0.08 mm3 , Fw 1242:24, orthorhombic, space group Aba2, a 15:78702,   b 19:80464, c 29:954 A, V 9365:22 A3 , Z 8, Dc 1:762 mg/m3 , F 0 0 0 4916, R 0:0629. X-ray diraction data were collected on a Siemens Smart CCD diractometer equipped with  graphite-monochromated Mo-Ka radiation (k 0:71073 A). Absorption correction was performed by the SADABS program. The structures were solved by the direct methods and subsequent dierence Fourier syntheses. Some of the 2-thiopheneacetic acid ligand in 14 are disordered. H atoms bonded to carbon were positioned geometrically. No H atoms were included for the water molecules. All non-hydrogen atoms except for O8w atom were rened anisotropically.
2
3

thiopheneacetic acid ligands in the present compounds can be classied as two types on the basis of their coordination modes of carboxylate groups. The rst mode is the l-oxo tridentate bridging fashion in which one of the carboxylate oxygen atoms bridges a pair of Ln atoms, while the other oxygen atom is coordinated in a syn fashion to one of them. In the second mode, the carboxylate group bridges a pair of Ln atoms in a synsyn OacO0 bidentate bridging fashion with two nearly equivalent CO distances of the carboxylate group. It is noticed that in the six crystallographically independent 2-thiopheneacetic acid ligands, only the O21C26O22 carboxylate group exhibits electron localization with C  O diering by 0.078 A. The neighbor chains are bridged by packing water molecules to form a layer-like structure through O H O hydrogen bonds (O3w()x,)y,z) O6w 2.93(1), O2w O6w 2.83(1), O1w O5w 2.62(1), O32(0.5)x, )0.5)y, z) O5w 3.02(1), O8w O4w 2.67(1),  O8w O3w 2.86(1) A) along the b axis if we arbitrarily  choose a cuto of 3.04 A for the OH O hydrogen bond. The crystal structure of present compounds constructed from the stacking of layers along the c direction. The emission spectra of crystalline samples for the present compounds and potassium salt of 2-thiopheneacetic acid ligand are shown in Fig. 2. The title complexes display very strong emission as compared with the anion of the ligand 2-thiopheneacetic in the same

R2 R6

R1

C25 C65 C66 O61 O21 Ce2 O3W O52 O2W C35 C56 O51 C55 R3 Ce1 O31 O62 C26

C15 O12 O22 C16 O11 O1W O32 C36 O42 C46 O41 C45

R5
S

R4

Fig. 1. Chain structure of 1 extending along the a axis. All hydrogen atoms and water molecules are omitted and thiophene rings are represented as solid circles and labeled as R for clarity. Selected distances: Ce1O31 2.443(5), Ce1O11 2.498(4), Ce1O52 2.522(4), Ce1O62 2.544(4), Ce1O41 2.576(5), Ce1O22 2.564(5), Ce1O2w 2.613(5), Ce1O1w 2.606(5), Ce1O21 2.762(5) Ce1O42 2.891(5), Ce1Ce2 4.2738(4), Ce2O42 2.392(5)a , Ce2O32 2.469(4)a , Ce2O61 2.473(5), Ce2O21 2.505(5), Ce2O12 2.554(5)a , Ce2O51 2.555(5), Ce2O3w 2.560(4) Ce2O52 2.573(4), Ce2O112.643(4)a , Ce2Ce14.3118(4)a . a: x 1=2, y 1=2, z.

L.-Z. Cai et al. / Inorganic Chemistry Communications 7 (2004) 611613

1200000

613

434.4 (4, ex = 365 nm)

1000000

and Natural Science Foundation of the Chinese Academy of Sciences (KJCX2-H3).

437.8 (1, ex = 357 nm)

800000

425.2 (3, ex = 355 nm) 421.7 (2, ex = 355 nm) 484.3 (anion of ligand, ex = 380 nm)

intensity / cps

References
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0 350 400 450 500 550 600 650 700 750 800 850 900 950

wavelength / nm

Fig. 2. Emission spectra of complexes 14 and potassium salt of 2thiopheneacetic acid ligand in solid state.

experimental environment. The emissions of the ve compounds can be assigned as pp transitions of the ligand. Generally, the rigidity of the ligand increases more in complex than that in its salt, so the enhanced uorescence eciency of the complexes is attributed to the more rigidity of the ligand coordination to Ln3 ion that eectively reduces the loss of energy. The shift of the emission is complicated. The high luminescence efciency indicates the four complexes may be good candidate for highly uorescent materials.

Acknowledgements This work was supported by National Natural Science Foundation of China (20001007, 20131020), Natural Science Foundation of Fujian Province (2003I031)