Sains Malaysiana 40(9)(2011): 999–1006

Synthesis, Characterization and Thermal Properties of Two Novel Lanthanide 2,2’-Biquinoline-4,4’-Dicarboxylate Complexes

(Sintesis, Pencirian dan Sifat Terma Dua Kompleks Lantanida 2,2’-bikuinolin-4,4’-dikarboksilat)

S. Zati-Hanani, R. Adnan*, A.F.A. Latip & C.S. Sipaut

Pusat Pengajian Sains Kimia, Universiti Sains Malaysia, 11800 Pulau Pinang, Malaysia

Received: 16 June 2010 / Accepted: 6 January 2011

ABSTRACT

Two new lanthanide coordination complexes with 2,2’-biquinoline-4,4’-dicarboxylic acid (H2bqda) and 1,10-phenanthroline (phen), [La2(Hbqda)2(bqda)2(phen)]n [1] and [Gd(bqda)1.5(phen)]n [2] were successfully synthesized and characterized. The complexes were obtained through hydrothermal method at 170oC for 3 days. The metal to acid to 1,10-phenanthroline ratio, 1:1:2 had been chosen to synthesize 1 and 2. The percentage yield for 1 and 2 was 68% and 75%, respectively calculated based on the starting lanthanide salt used. The yellow coloured complexes were found to be stable at room temperature and insoluble in organic solvents. The complexes obtained were characterized by elemental analysis (CHN), infrared spectroscopy (FTIR) and thermogravimetric (TGA) analysis. The FTIR spectra of these complexes confirm the complexation had taken place by the existence of COO- symmetric and asymmetric stretching peaks at 1385 and 1542-1532 cm-1, respectively.

Keywords: 1,10-phenanthroline; 2,2’-biquinoline-4,4’-dicarboxylic acid; hydrothermal method; lanthanide

ABSTRAK

Dua kompleks koordinatan baru lantanida dengan asid 2,2’-bikuinolin-4,4’-dikarboksilik (H2bqda) dan 1,10-fenantrolina (phen), [La2(Hbqda)2(bqda)2(phen)]n [1] dan [Gd(bqda)1.5(phen)]n [2] telah berjaya disintesis dan dicirikan. Kompleks ini telah diperoleh melalui kaedah hidroterma pada suhu 170oC selama 3 hari. Nisbah logam kepada asid kepada 1,10-fenantrolin, 1:1:2, telah dipilih untuk mensintesiskan 1 dan 2. Peratus hasil bagi 1 dan 2 masing-masing adalah 68% dan 75% dikira berdasarkan garam lantanida yang digunakan. Kompleks berwarna kuning ini didapati stabil pada suhu bilik dan tidak larut dalam pelarut organik. Kompleks yang diperoleh telah dicirikan menggunakan analisis unsur (CHN), spektroskopi inframerah (FTIR) dan analisis termogravimetri (TGA). Spektra FTIR bagi kompleks membuktikan pengkompleksan telah berlaku dengan kewujudan puncak simetrik dan asimetrik COO- masing-masing pada 1385 dan 1542-1532 cm-1.

Kata kunci: asid 2,2’-bikuinolin-4,4’-dikarboksilik; kaedah hidroterma; lantanida; 1,10-fenantrolina

REFERENCES

Chen, X.L., Wang, J.J., Hu, H.M., Fu, F., Shu, H.M., Yang, M.L., Xue, G.L., Du, C.Q. & Yao, Y.J. 2007. Hydrothermal syntheses, crystal structures and luminescence of two novel metal-organic frameworks. Zeitschrift Fur Anorganische Und Allgemeine Chemie 633: 2053-2058.

Cho, J., Lough, A. & Kim, J. 2003. Monomeric and polymeric copper (II) hexaaza macrocyclic complexes with btc anions (btc= 1, 2, 4, 5-benzenetetracarboxylic acid). Inorganica Chimica Acta 342: 305-310.

Dai, P.X., Yang, E.C., Wang, X.G. & Zhao, X.J. 2008. Synthesis, crystal structures and fluorescent properties of two 2,2’-biquinoline-4,4’-dicarboxylate-based cadmium(II) and cobalt(II) complexes. Zeitschrift Fur Anorganische Und Allgemeine Chemie 634: 1581-1586.

Deacon, G. & Phillips, R. 1980. Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination. Coordination Chemistry Reviews 33: 227-250.

Du, M., Zou, R., Zhong, R. & Xu, Q. 2008. Hydrothermal synthesis, crystal structures and properties of new Fe(II), Co(II), Ni(II), and Zn(II) complexes with 6-quinolinecarboxylate: Interplay of coordinative and noncovalent interactions. Inorganica Chimica Acta 361: 1555-1561.

Fang, Q.R., Zhu, G.S., Shi, X., Wu, G., Tian, G., Wang, R.W. & Qiu, S.L. 2004. Synthesis, structure and fluorescence of a novel three-dimensional inorganic-organic hybrid polymer constructed from trimetallic clusters and mixed carboxylate ligands. Journal of Solid State Chemistry 177: 1060-1066.

Hill, R.J., Long, D.L., Hubberstey, P., Schroeder, M. & Champness, N. R. 2005. Lanthanide co-ordination frameworks: Opportunities and diversity. Journal of Solid State Chemistry 178: 2414-2419.

Hu, M., Wang, Q., Xu, G.F., Deng, G.R., Yang, G.M., Yu, M. & Zhang, Y.H. 2007. First examples of ternary lanthanide 2,2’ -bipyridine-3,3’-dicarboxylate coordination polymers with zigzag chains structures assembled from lanthanide ions, 2,2’-bipyridine-3,3’-dicarboxylate and 1,10-phenanthroline. Inorganica Chimica Acta 360: 1684-1690.

Janiak, C. 2003. Engineering coordination polymers towards applications. Dalton Transactions 2003: 2781-2804.

Kongshaug, K. & Fjellvåg, H. 2003. Novel coordination polymers based on nickel (II) and 2, 6-naphthalenedicarboxylate. Solid State Sciences 5: 303-310.

Liu, C.B., Zheng, X.J., Yang, Y.Y. & Jin, L.P. 2005. Template-assisted assembly of porous lanthanide coordination polymers with 2-aminoterephthalic acid. Inorganic Chemistry Communications 8: 1045-1048.

Liu, C., Gao, S., Jin, X. & Kou, H. 2002. Hydrothermal syntheses and crystal structures of two-dimensional (2D) layered vanadium oxide complexes: M(bipy)(H2O)V2O6 (M= Ni, Co, bipy= bipyridine) and [Ni(bipy)2V6O17]. Journal of the Chemical Society, Dalton Transactions 2002: 598-601.

Nakamoto, K. 2009. Infrared and Raman Spectra of Inorganic and Coordination Compounds, Applications in Coordination, Organometallic, and Bioinorganic Chemistry. Sixth ed. New York: Wiley-Interscience.

Pan, L., Zheng, N.W., Wu, Y.G., Nan, S., Yang, R.Y., Huang, X.Y. & Li, J. 2001. Synthesis, characterization and structural transformation of a condensed rare earth metal coordination polymer. Inorganic Chemistry 40: 828-830.

Qin, C., Wang, X.L., Wang, E.B. & Xu, L. 2006. Synthesis, structures and thermal properties of three new two-dimensional coordination networks assembled by lanthanide salts and carboxylate ligand. Inorganica Chimica Acta 359: 417-423.

Qin, C., Wang, X.-L., Wang, E.-B. & Su, Z.-M. 2005. A series of three-dimensional lanthanide coordination polymers with rutile and unprecedented rutile-related topologies. Inorganic Chemistry 44: 7122-7129.

Ren, N., Zhang, J., Wang, R. & Wang, S. 2006. Synthesis, crystal structure and thermal decomposition process of complex [Sm(BA)3phen]2. Journal of the Chinese Chemical Society 53: 293-298.

Robson, R. 2000. A net-based approach to coordination polymers. Journal of the Chemical Society, Dalton Transactions 2000: 3735-3744.

Rogan, J., Poleti, D., Karanovi, L., Bogdanovi, G., Spasojevi-de Biré, A. & Petrovi, D. 2000. Mixed ligand Co(II), Ni(II) and Cu(II) complexes containing terephthalato ligands. Crystal structures of diaqua(2, 2’-dipyridylamine)(terephthalato) metal(II) trihydrates (metal = cobalt or nickel). Polyhedron 19: 1415-1421.

Rowsell, J. & Yaghi, O. 2004. Metal-organic frameworks: a new class of porous materials. Microporous and Mesoporous Materials 73: 3-14.

Si, S.F., Wang, R.J. & Li, Y.D. 2003. Synthesis and crystal structure of three dimensional complex from copper(II) and 1,2,4,5-benzenetetracarboxylate. Inorganic Chemistry Communications 6: 1152-1155.

Sun, D., Cao, R., Bi, W., Weng, J., Hong, M. & Liang, Y. 2004. Syntheses and characterizations of a series of silver-carboxylate polymers. Inorganica Chimica Acta 357: 991-1001.

Wan, Y., Jin, L., Wang, K., Zhang, L., Zheng, X. & Lu, S. 2002. Hydrothermal synthesis and structural studies of novel 2-D lanthanide coordination polymers with phthalic acid. New Journal of Chemistry 26: 1590-1596.

Wan, Y., Zhang, L. & Jin, L. 2003. Three new lanthanide coordination polymers containing isophthalate and 1, 10-phenanthroline. Journal of Molecular Structure 658: 253-260.

Wu, J.Y., Yeh, T.T., Wen, Y.S., Twu, J. & Lu, K.L. 2006. Unusual robust luminescent porous frameworks self-assembled from lanthanide ions and 2, 2’-bipyridine-4, 4’-dicarboxylate. Crystal Growth & Design 6: 467-473.

Xiel, J.L. 2009. Two-dimensional metal-organic framework [Zn(bqdc)](n) (bqdc=2,2 ‘-biquinoline-4,4 ‘-dicarboxylate): Synthesis, crystal structure and spectral characterization. Zeitschrift Fur Anorganische Und Allgemeine Chemie 635: 384-388.

Xu, H., Zheng, N., Jin, X., Yang, R. & Li, Z. 2003. A new microporous structure constructed by a lanthanide-carboxylate coordination polymer. Journal of Molecular Structure 654: 183-186.

Ye, J.W., Zhang, P., Ye, K.Q., Zhang, H.Y., Jiang, S.M., Ye, L., Yang, G.D. & Wang, Y. 2006. Design and synthesis of four coordination polymers generated from 2,2’-biquinoline-4,4’-dicarboxylate and aromatic bidentate ligands. Journal of Solid State Chemistry 179: 438-449.

Ye, Q., Chen, X., Song, Y., Wang, X., Zhang, J., Xiong, R., Fun, H. & You, X. 2005. A blue fluorescent Cd (II) coordination polymer with 3, 5-diaminobenzoic acid ligand: synthesis, crystal structure and fluorescent property. Inorganica Chimica Acta 358: 1258-1262.

Yong, G.-P., Wang, Z.-Y. & Cui, Y. 2004. Synthesis, structural characterization and properties of copper(II) and zinc(II) coordination polymers with a new bridging chelating ligand. European Journal of Inorganic Chemistry 2004: 4317-4323.

Zhai, B., Shen, W.Z., Chen, X.Y., Song, H.B., Shi, W. & Cheng, P. 2006. Terminal ligand effect on the structure variation of copper(II) complexes. Inorganic Chemistry Communications 9: 1293-1296.

Zhang, G.Q., Wang, Q., Qian, Y., Yang, G.Q. & Ma, J.S. 2006. Synthesis, characterization and photoluminescence properties of two new europium(III) coordination polymers with 3D open framework. Journal of Molecular Structure 796: 187-194.

Zhang, Y., Yang, J., Li, G.D., Zhang, F. & Chen, J.S. 2008a. Synthesis, structures and photoluminescence of two Er(III) coordination polymers. Journal of Coordination Chemistry 61: 945-955.

Zhang, Y.N., Liu, J.Q., Wang, T., Wen, G.L., Yang, G.P., Wang, Y.Y. & Shi, Q. Z. 2008b. Design and syntheses of two novel Mn(II) and Cu(II) complexes with 2,2-biquinoline-4,4’- dicarboxylate and N-containing bidentate co-ligand. Journal of Molecular Structure 878: 116-123.

*Corresponding author; email: r_adnan@usm.my