Inorganic Chemistry Communications 7 (2004) 611–613

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Inorganic Chemistry Communications 7 (2004) 611–613 www.elsevier.com/locate/inoche 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 2

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  Syntheses, structures and luminescent properties of four new1D lanthanide complexes with 2-thiopheneacetic acid ligand q 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 2004Available online 19 March 2004 Abstract Four complexes, Ln 2 (C 6 H 5 SO 2 ) 6 (H 2 O) 3 Á 2.25H 2 O (C 6 H 5 SO 2 ¼ 2-thiopheneacetic acid, Ln ¼ Ce ( 1 ), Pr ( 2 ), Nd ( 3 ), Sm ( 4 )),have been synthesized with hydrothermal route. The X-ray diffraction analyses reveal that they are characterized by the 1D structureand fluorescence studies show they display interesting luminescent properties in solid state. Ó 2004 Elsevier B.V. All rights reserved. Keywords: Crystal structure; Luminescence; Lanthanide; 2-thiopheneacetic acid In the past few years, lanthanide compounds have at-tached extremely interesting because they not only possespotentialpropertiesinluminescentandmagnetic,butalsogenerate diversities of structures by selecting differentbridging ligands [1]. A lot of work have been done to de-sign and synthesize lanthanide chelates with good lumi-nescentproperties[2–5].Chelatingagentscommonlyusedfor these compounds include b -diketonates, [4,6] pyridin-ecarboxylic acids, [2,5,7] benzene carboxylic acid [3] andotherheteroaromatics[8].Inviewofthehighluminescencequantum yields of the europium salt of 4-(thin-2-yl)pyri-dine-2,6-dicarboxylic acid [8], we select 2-thiopheneaceticacid as bridging ligand-to-investigate the influence on thelanthanideluminescencebyligandtometalenergytransfermechanism.Wereporthereinthesynthesesandstructuresof four new lanthanide complexes with 2-thiopheneaceticacid using hydrothermal technique, to the best of ourknowledge, the metal complexes that involve 2-thioph-eneacetic acid as the bridging ligand have not yet beenexperimentally or theoretically described so far.The prismatic crystals of compounds 1–4 ,Ln 2 (C 6 H 5 SO 2 ) 6 (H 2 O) 3 Á 2.25H 2 O 1 , were synthesized by q 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 H 2 O, then Me 4 NOH was added dropwise to the above solution until pH was 7–8,finally, 0.5 mmol of salt of lanthanide (Ce(NO 3 ) 3 Á 6H 2 O for 1 , LnCl 3 Á 6H 2 O for 2–4 ) was added. The reaction mixtures were heated at 170 ° C in aTeflon-lined stainless steel autoclave for 5 days. The filtrates were left to stand in atmosphere for several days then crystals suitable for X-raydetermination 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 (cm À 1 , KBr): 1 : m as (COO):1542.79, m s (COO): 1384.66–1488.80; 2 : m as (COO): 1542.79, m s (COO): 1384.66–1488.80; 3 : m as (COO): 1546.65, m s (COO): 1390.44–1488.80; 4 : m as (COO):1548.58, m s (COO): 1388.51–1488.80.1 mmol of 2-thiopheneacetic acid was dissolved in 10 ml of H 2 O, then Me 4 NOH was added dropwise to theabove solution until pH was 7–8, finally, 0.5 mmol of salt of lanthanide (Ce(NO 3 ) 3 Á 6H 2 O for 1, LnCl 3 Á 6H 2 O for 2–4 ) was added. The reactionmixtures were heated at 170 ° C in a Teflon-lined stainless steel autoclave for 5 days. The filtrates were left to stand in atmosphere for several days thencrystals 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(cm À 1 , KBr): 1 : m as (COO): 1542.79, m s (COO): 1384.66–1488.80; 2 : m as (COO): 1542.79, m s (COO): 1384.66–1488.80; 3 : m as (COO): 1546.65, m s (COO):1390.44–1488.80; 4 : m as (COO): 1548.58, m s (COO): 1388.51–1488.80.1387-7003/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.doi:10.1016/j.inoche.2004.02.015www.elsevier.com/locate/inocheInorganic Chemistry Communications 7 (2004) 611–613  the reaction of 2-thiopheneacetic acid, salt of trivalentlanthanide, Me 4 NOH and H 2 O under hydrothermalconditions. The compounds are very stable in air atambient temperature. Single crystal X-ray analysis 2 of present complexes reveals that they are isomorphousand compound 1 is discussed in detail. Each structure of the complexes consists of two crystallographically in-dependent Ln (III) ions (Ln1 and Ln2), six crystallo-graphically independent 2-thiopheneacetic acid ligands,three coordinated water molecules, and packing watermolecules, as shown in Fig. 1. The Ln1 ion is decaco-ordinated with two water molecules and eight oxygenatoms from six 2-thiopheneacetic acid ligands. While theLn2 ion is nine-coordinated, consisting of a water mol-ecule and eight oxygen atoms from the carboxylategroups of six 2-thiopheneacetic acid ligands. The ge-ometry of the Ln2 center can be related to a tricappedtrigonal prism with the two outer triangular facesformed 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 Ln–O bonddistances (Ce1–O42 ¼ 2.891(5), Pr1–O41 ¼ 2.924(5),Nd1–O42 ¼ 2.901(6), Sm1–O21 ¼ 2.840(4)  A) in 1–4 isobviously longer than those in lanthanide compoundsbridged by carboxylate group [2], [11] and can be re-garded as a weak interaction [12]. The rest of Ln–Obond distances ranging from 2.363(4) to 2.762(5)  A inthe present compounds are normal as compared withlanthanide carboxylates.The Ln1 and Ln2 atoms in 1–4 are triply bridged bythree 2-thiopheneacetic acid ligands to form an infinitechain extending along the [100] direction with alternateintra-chain Ln ÁÁÁ Ln distances (Ln ÁÁÁ Ln ¼ 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 2-thiopheneacetic acid ligands in the present compoundscan be classified as two types on the basis of their co-ordination modes of carboxylate groups. The first modeis the l -oxo tridentate bridging fashion in which one of the carboxylate oxygen atoms bridges a pair of Ln at-oms, while the other oxygen atom is coordinated in a syn fashion to one of them. In the second mode, the car-boxylate group bridges a pair of Ln atoms in a syn–syn  – O–  ac  –O 0 bidentate bridging fashion with two nearlyequivalent C–O distances of the carboxylate group. It isnoticed that in the six crystallographically independent2-thiopheneacetic acid ligands, only the O21–C26–O22carboxylate group exhibits electron localization with C– O differing by 0.078  A.The neighbor chains are bridged by packing watermolecules to form a layer-like structure through O– H ÁÁÁ O hydrogen bonds (O3w( ) x , )  y,z ) ÁÁÁ O6w 2.93(1),O2w ÁÁÁ O6w 2.83(1), O1w ÁÁÁ O5w 2.62(1), O32(0.5 ) x , ) 0.5 )  y, z ) ÁÁÁ O5w 3.02(1), O8w ÁÁÁ O4w 2.67(1),O8w ÁÁÁ O3w 2.86(1)  A) along the b axis if we arbitrarilychoose a cutoff of 3.04  A for the O–H ÁÁÁ O hydrogenbond. The crystal structure of present compoundsconstructed from the stacking of layers along the c direction.The emission spectra of crystalline samples for thepresent compounds and potassium salt of 2-thiophene-acetic acid ligand are shown in Fig. 2. The title com-plexes display very strong emission as compared withthe anion of the ligand 2-thiopheneacetic in the same 2 Crystal data: 1 : crystal dimensions 0.36  0.14  0.08 mm 3 ,  F  w ¼ 1221 : 78, orthorhombic, space group Aba2 , a ¼ 16 : 070, b ¼ 19 : 9293 ð 4 Þ , c ¼ 29 : 9953 ð 7 Þ , V   ¼ 9606 : 5 ð 3 Þ  A 3 , Z  ¼ 8, D c ¼ 1 : 690mg/m 3 , F  ð 000 Þ ¼ 4852, R ¼ 0 : 0633. 2 : crystal dimensions0.26  0.20  0.06 mm 3 , F  w ¼ 1223 : 36, orthorhombic, space group Aba2 , a ¼ 15 : 998 ð 1 Þ , b ¼ 19 : 883 ð 1 Þ , c ¼ 29 : 962 ð 2 Þ  A, V   ¼ 9530 ð 1 Þ  A 3 , Z  ¼ 8, D c ¼ 1 : 705 mg/m 3 , F  ð 000 Þ ¼ 4868, R ¼ 0 : 0739. 3 : crystaldimensions 0.56  0.14  0.14 mm 3 , F  w ¼ 1230 : 02, orthorhombic,space group Aba2 , a ¼ 16 : 070 ð 1 Þ , b ¼ 19 : 9293 ð 4 Þ , c ¼ 29 : 9953 ð 7 Þ  A, V   ¼ 9606 : 5 ð 3 Þ  A 3 , Z  ¼ 8, D c ¼ 1 : 701 mg/m 3 , F  ð 000 Þ ¼ 4884,  R ¼ 0 : 0632. 4 : crystal dimensions 0.36  0.16  0.08 mm 3 ,  F  w ¼ 1242 : 24, orthorhombic, space group Aba2 , a ¼ 15 : 7870 ð 2 Þ , b ¼ 19 : 8046 ð 4 Þ , c ¼ 29 : 954  A, V   ¼ 9365 : 2 ð 2 Þ  A 3 , Z  ¼ 8, D c ¼ 1 : 762mg/m 3 , F  ð 000 Þ ¼ 4916, R ¼ 0 : 0629. X-ray diffraction data werecollected on a Siemens Smart CCD diffractometer equipped withgraphite-monochromated Mo-K a radiation ( k ¼ 0 : 71073  A). Absorp-tion correction was performed by the SADABS program. Thestructures were solved by the direct methods and subsequent differenceFourier syntheses. Some of the 2-thiopheneacetic acid ligand in 1–4 aredisordered. H atoms bonded to carbon were positioned geometrically.No H atoms were included for the water molecules. All non-hydrogenatoms except for O8w atom were refined anisotropically. C35R3O32R1C36C65O12O31C66C16O62C15O61R6O11O42C55O52Ce1C56C46C45R5Ce2O41O51O22O21C26R4O1WC25O2WO3WR2 S R Fig. 1. Chain structure of  1 extending along the a axis. All hydrogenatoms and water molecules are omitted and thiophene rings are rep-resented as solid circles and labeled as R for clarity. Selected distances:Ce1–O31 2.443(5), Ce1–O11 2.498(4), Ce1–O52 2.522(4), Ce1–O622.544(4), Ce1–O41 2.576(5), Ce1–O22 2.564(5), Ce1–O2w 2.613(5),Ce1–O1w 2.606(5), Ce1–O21 2.762(5) Ce1–O42 2.891(5), Ce1–Ce24.2738(4), Ce2–O42 2.392(5) a , Ce2–O32 2.469(4) a , Ce2–O61 2.473(5),Ce2–O21 2.505(5), Ce2–O12 2.554(5) a , Ce2–O51 2.555(5), Ce2–O3w2.560(4) Ce2–O52 2.573(4), Ce2–O112.643(4) a , Ce2–Ce14.3118(4) a . a:  x À 1 = 2, À  y  þ 1 = 2, z .612 L.-Z. Cai et al. / Inorganic Chemistry Communications 7 (2004) 611–613  experimental environment. The emissions of the fivecompounds can be assigned as p  –  p à transitions of theligand. Generally, the rigidity of the ligand increasesmore in complex than that in its salt, so the enhancedfluorescence efficiency of the complexes is attributed tothe more rigidity of the ligand coordination to Ln 3 þ ionthat effectively reduces the loss of energy. The shift of the emission is complicated. The high luminescence ef-ficiency indicates the four complexes may be good can-didate for highly fluorescent materials. Acknowledgements This work was supported by National Natural Sci-ence Foundation of China (20001007, 20131020), Nat-ural Science Foundation of Fujian Province (2003I031)and Natural Science Foundation of the Chinese Acad-emy of Sciences (KJCX2-H3). References [1] (a) G.F. de Sa, O.L. Malta, C.D. Donega, A.M. Simas, R.L.Longo;, P.A. Santa-Cruz, E.F. da Silva, Coord. Chem. Rev.196 (2000) 165;(b) J. Kido, Y. Okamoto, Chem. Rev. 102 (2002) 2357;(c) S. Richardson, Chem. Rev. 82 (1982) 541;(d) B. Yan, H.J. Zhang, S.B. Wang, J.Z. Ni, Mater. Chem. Phys.52 (1997) 151;(e) B. Yan, H.J. Zhang, S.B. Wang, J.Z. Ni, Mater. Res. Bull. 33(1998) 1511;(f) C.F. Meares, T.G. Wensel, Acc. Chem. Res. 17 (1984) 202.[2] L. Ma, O.R. Evans, B.M. Foxman, W.b. Lin, Inorg. Chem. 38(1999) 5837.[3] T.M. Reineke, M. Eddaoudi, M. Fehr, D. Kelley, O.M. Yaghi, J.Am. Chem. Soc. 121 (1999) 1651.[4] J.b. Yu, H.J. Zhang, L.S. Fu, R.P. Deng, L. Zhou, H.R. Li, F.Y.Liu, H.L. Fu, Inorg. Chem. Commun. 6 (2003) 852.[5] (a) A. Fernandes, J. Jaud, J. Dexpert-Ghys, C. Brouca-Cabar-recq, Polyhedron 20 (2001) 2385;(b) J.G. Mao, H.J. Zhang, J.Z. Ni, S.B. Wang, T.C.W. Mak,Polyhedron 17 (1998) 2888;(c) J. Kay, W.M. Jerry, M.D. Glick, Inorg. Chem. 11 (1972) 2818.[6] (a) C.Y. Su, B.S. Kang, H.Q. Liu, Q.G. Wang, Z.N. Chen, Z.L.Lu, Y.X. Tong, T.C.W. Mak, Inorg. Chem. 38 (1999) 1374;(b) B. Alpha, J.M. Lehn, G. Mathis, Angew. Chem. Int. Ed. 26(1987) 266;(c) R. Ziessel, M. Maestri, L. Prodi, V. Balzani, A. Dorsselaer,Inorg. Chem. 32 (1993) 1237.[7] B. Yan, Q.Y. Xie, Inorg. Chem. Commun. 6 (2003) 1448.[8] M. Latva, H. Takalo, V.M. Mukkala, C. Matachescu, J.C.Rodriguez-Ubis, J. Kankare, J. Lumin. 75 (1997) 149.[11] (a) J. Kay, W.M. Jerry, M.D. Glick, Inorg. Chem. 11 (1972) 2818;(b) P.C. Junk, C.J. Kepert, W.M. Lu, B.W. Skelton, A.H. White,Aust. J. Chem. 52 (1999) 437.[12] W.M. Jerry, D.G. Milton, W.A. Baker, J. Am. Chem. Soc. 94(1972) 1858. 350400450500550600650700750800850900950020000040000060000080000010000001200000 484.3 (anion of ligand, λ  ex = 380 nm)425.2 ( 3 , λ  ex = 355 nm)421.7 ( 2 , λ  ex = 355 nm)437.8 ( 1 , λ  ex = 357 nm)434.4 ( 4 , λ  ex = 365 nm)    i  n   t  e  n  s   i   t  y   /  c  p  s wavelength / nm Fig. 2. Emission spectra of complexes 1–4 and potassium salt of 2-thiopheneacetic acid ligand in solid state. L.-Z. Cai et al. / Inorganic Chemistry Communications 7 (2004) 611–613 613
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