Solvothermal synthesis, structure, and luminescent properties of a series of 3D lanthanide carbonate frameworks


  • Phailyn Khemthong Department of Chemistry, Faculty of Science, Naresuan University, Muang, Phitsanulok 65000, Thailand
  • Filip Kielar Department of Chemistry, Faculty of Science, Naresuan University, Muang, Phitsanulok 65000, Thailand
  • Kittipong Chainok Department of Physics, Faculty of Science and Technology, Thammasat University, Rangsit Campus, Khlong Luang, Patumthani 12120, Thailand


carbonate, crystallography, crystal structure, lanthanide, luminescence, solvothermal synthesis


A series of three-dimensional (3D) lanthanide carbonate coordination polymers [Ln(μ5-CO3)(μ2-OH)], LnIII = Pr (1Pr), Nd (2Nd), Sm (3Sm), Eu (4Eu), Gd (5Gd), Tb (6Tb) and Dy (7Dy), has been synthesized using solvothermal conditions and characterized by spectroscopic methods.  Structures of compounds 1Pr-3Sm were solved from single crystal X-ray diffraction (SCXRD) data, whereas microcrystals of compounds 4Eu-7Dy were not of sufficient quality for SCXRD analysis.  Therefore, conventional powder X-ray diffraction (PXRD) and elemental analysis have been used to verify the phase purity. SCXRD analysis revealed that compounds 1Pr-3Sm are isostructural and crystallize in the orthorhombic space group Pnma with four formula units per unit cell.  In the crystal structure, each LnIII cation is bridged by five μ522211-CO32− and two μ2-OH ligands forming a neutral 3D framework.  The luminescence properties of compounds 4Eu and 6Tb were investigated in the solid state at room temperature.


Andrews, P. C., Beck, T., Forsyth, C. M., Fraser, B. H., Junk, P. C., Massi, M., & Roesky, P. W. (2007). Templated assembly of a µ6-CO32− dodecanuclear lanthanum dibenzoylmethanide hydroxido cluster with concomitant formation of phenylglyoxylate. Dalton Transactions, Issue 48, 5651-5654. DOI: 10.1039/B710534G

Bag, P., Dutta, S., Biswas, P., Maji, S. K., Flörke, U., & Nag, K. (2012). Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with µ3-η2:η2:η2 bonding. Dalton Transactions, Issue 41, 3414-3423. DOI: 10.1039/C2DT12221A

Bruker (2014). APEX2, SAINT, XPREP and SADABS. Madison, Wisconsin, USA: Bruker AXS Inc.

Bünzli, J.-C. G., & Piguet, C. (2005). Taking advantage of luminescent lanthanide ions. Chemical Society Reviews, 34, 1048-1077. DOI: 10.1039/B406082M

Calvez, G., Daiguebonne, C., & Guillou, O. (2011). Unprecedented lanthanide-containing coordination polymers constructed from hexanuclear molecular building blocks: {[Ln6O(OH)8](NO3)2(bdc)(Hbdc)2·2NO3·H2bdc}∞. Inorganic Chemistry, 50(7), 2851-2858. DOI: 10.1021/ic102036q

Chesman, A. S. R., Turner, D. R., Moubaraki, B., Murray, K. S., Deacon, G. B., & Batten, S. R. (2012). Tetradecanuclear polycarbonatolanthanoid clusters: diverse coordination modes of carbonate providing access to novel core geometries. Dalton Transactions, Issue 41, 10903-10909. DOI: 10.1039/C2DT31101A

Dang, S., Zhang, J. H., Sun, Z. M., & Zhang, H. (2012). Luminescent lanthanide metal-organic frameworks with a large SHG response. Chemical Communications, 48(90), 11139-11141. DOI: 10.1039/C2CC35432B

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K., & Puschmann, H. (2009). OLEX2: a complete structure solution, refinement and analysis program. Journal of Applied Crystallography, 42(2), 339-341. DOI: 10.1107/S0021889808042726

Fang, X., Anderson, T. M., Neiwert, W. A., & Hill, C. L. (2003). Yttrium polyoxometalates: synthesis and characterization of a carbonate-encapsulated sandwich-type complex. Inorganic Chemistry, 42(26), 8600-8602. DOI: 10.1021/ic0350842

Gass, I. A., Moubaraki, B., Langley, S. K., Batten, S. R., & Murray, K. S. (2012). A π–π 3D network of tetranuclear μ2/μ3-carbonato Dy(III) bis-pyrazolylpyridine clusters showing single molecule magnetism features. Chemical Communications, 48(15), 2089-2091. DOI: 10.1039/C2CC16946K

Gu, J. Z., Wu, J., Lv, D. Y., Tang, Y., Zhu, K., & Wu, J. (2013). Lanthanide coordination polymers based on 5-(2′-carboxylphenyl) nicotinate: syntheses, structure diversity, dehydration/hydration, luminescence and magnetic properties. Dalton Transactions, Issue 42, 4822-4830. DOI: 10.1039/C2DT32674D

Gunanathan, C., Diskin-Posner, Y., &Milstein, D. (2010). Lanthanide-organic framework of a rigid bis-Gd complex: composed by carbonate ions spacers. Crystal Growth and Design, 10(10), 4235-4239. DOI: 10.1021/cg100843k

Guo, Z., Song, X., Lei, H., Wang, H., Su, S., Xu, H., . . . Chen, B. (2015). A ketone functionalized luminescent terbium metal-organic framework for sensing of small molecules. Chemical Communications, 51, 376-379. DOI: 10.1039/C4CC06729K

Han, J. W., & Hill, C. L. (2007). A coordination network that catalyzes O2-based oxidations. Journal of the American Chemical Society, 129(49), 15094-15095. DOI: 10.1021/ja069319v

Hooper, T. N., Inglis, R., Palacios, M. A., Nichol, G. S., Pitak, M. B., Coles, S. J., . . . Brechin, E. K. (2014). CO2 as a reaction ingredient for the construction of metal cages: a carbonate-panelled [Gd6Cu3] tridiminished icosahedron. Chemical Communications, 50(26), 3498-3500. DOI: 10.1039/C4CC00141A

Hutchings, A.-J., Habib, F., Holmberg, R. J., Korobkov, I., & Murugesu, M. (2014). Structural rearrangement through lanthanide contraction in dinuclear complexes. Inorganic Chemistry, 53(4), 2102-2112. DOI: 10.1021/ic402682r

Langley, S. K., Moubaraki, B., & Murray, K. S. (2012). Magnetic properties of hexanuclear lanthanide(III) clusters incorporating a central μ6-carbonate ligand derived from atmospheric CO2 fixation. Inorganic Chemistry, 51(7), 3947-3949. DOI: 10.1021/ic3002724

Langley, S. K., Chilton, N. F., Moubaraki, B., & Murray, K. S. (2013). Anisotropy barrier enhancement via ligand substitution in tetranuclear {CoIII2LnIII2} single molecule magnets. Chemical Communications, 49(62), 6965-6967. DOI: 10.1039/C3CC44037K

Langley, S. K., Wielechowski, D. P., Vieru, V., Chilton, N. F., Moubaraki, B., Chibotaru, L. F., & Murray, K. S. (2014). Modulation of slow magnetic relaxation by tuning magnetic exchange in {Cr2Dy2} single molecule magnets. Chemical Science, 5, 3246-3256. DOI: 10.1039/C4SC01239A

Langley, S. K., Wielechowski, D. P., Vieru, V., Chilton, N. F., Moubaraki, B., Chibotaru, L. F., & Murray, K. S. (2015). The first 4d/4f single-molecule magnet containing a {RuIII2DyIII2} core. Chemical Communications, 51, 2044-2047. DOI: 10.1039/C4CC08811E

Li, Y. F., Jin, L., Li, D. P., & Zhang, L. (2008). NdO(NO3). Acta Crystallographica Section E: Structure Reports Online, E64, i81. DOI: 10.1107/S1600536808036295

Li, Q. Y., Yang, G. W., Tang, X. Y., Ma, Y. S., Yao, W., Zhou, F., . . . Zhou, H. (2010). Constructions of a set of new lanthanide-based coordination polymers with Hatza Ligands (Hatza = 5-aminotetrazole-1-acetic acid). Crystal Growth and Design, 10(1), 165-170. DOI: 10.1021/cg900807t

Long, D. L., Blake, A. J., Champness, N. R., Wilson, C., & Schröder, M. (2001). Unprecedented seven- and eight-connected lanthanide coordination networks. Angewandte Chemie International Edition, 40(13), 2443-2447. DOI: 10.1002/1521-3773(20010702)40:13<2443::AID-ANIE2443>3.0.CO;2-C

Long, D. L., Blake, A. J., Champness, N. R., Wilson, C., & Schröder, M. (2002). Constructing terbium coordination polymers of 4,4′-bipyridine-N,N′-dioxide by means of diffusion solvent mixtures. Chemistry – A European Journal, 8(9), 2026-2033. DOI: 10.1002/1521-3765(20020503)8:9<2026::AID-CHEM2026>3.0.CO;2-8

Long, J., Rouquette, J., Thibaud, J. M., Ferreira, R. A. S., Carlos, L. D., Donnadieu, B., . . . Larionova, J. (2015). A high-temperature molecular ferroelectric Zn/Dy complex exhibiting single-ion-magnet behavior and lanthanide luminescence. Angewandte Chemie International Edition, 127(7), 2236-2240. DOI: 10.1002/ange.201410523

Lu, W. G., Jiang, L., & Lu, T. B. (2010). Lanthanide contraction and temperature-dependent structures of lanthanide coordination polymers with imidazole-4,5-dicarboxylate and oxalate. Crystal Growth and Design, 10(10), 4310-4318. DOI: 10.1021/cg100196j

Ma, X., Li, X., Cha, Y. E., & Jin, L. P. (2012). Highly thermostable one-dimensional lanthanide(III) coordination polymers constructed from benzimidazole-5,6-dicarboxylic acid and 1,10-phenanthroline: synthesis, structure, and tunable white-light emission. Crystal Growth and Design, 12(11), 5227-5232. DOI: 10.1021/cg300932a

Marchal, C., Filinchuk, Y., Chen, X. Y., Imbert, D., & Mazzanti, M. (2009). Lanthanide-based coordination polymers assembled by a flexible multidentate linker: design, structure, photophysical properties, and dynamic solid-state behavior. Chemistry – A European Journal, 15(21), 5273-5288. DOI: 10.1002/chem.200802589

Martínez-Calvo, M., Kotova, O., Möbius, M. E., Bell, A. P., McCabe, T., Boland, J. J., & Gunnlaugsson, T. (2015). Healable luminescent self-assembly supramolecular metallogels possessing lanthanide (Eu/Tb) dependent rheological and morphological properties. Journal of the American Chemical Society, 137(5), 1983-1992. DOI: 10.1021/ja511799n

Matthes, P. R., Nitsch, J., Kuzmanoski, A., Feldmann, C., Steffen, A., Marder, T. B., & Müller-Buschbaum, K. (2013). The series of rare earth complexes [Ln2Cl6(μ-4,4′-bipy)(py)6], Ln=Y, Pr, Nd, Sm-Yb: A molecular model system for luminescence properties in MOFs based on LnCl3 and 4,4′ bipyridine. Chemistry – A European Journal, 19(51), 17369-17378. DOI: 10.1002/chem.201302504

Mcmahon, B., Mauer, P., Mccoy, C. P., Lee, T C., & Gunnlaugsson, T. (2009). Selective imaging of damaged bone structure (microcracks) using a targeting supramolecular Eu(III) complex as a lanthanide luminescent contrast agent. Journal of the American Chemical Society, 131(48), 17542-17543. DOI: 10.1021/ja908006r

Mishra, A., Wernsdorfer, W., Abboud, K. A., & Christou, G. (2004). Initial observation of magnetization hysteresis and quantum tunneling in mixed manganese-lanthanide single-molecule magnets. Journal of the American Chemical Society, 126(48), 15648-15649. DOI: 10.1021/ja0452727

Mu, W., Huang, X., Zhong, R., Xia, W., Liu, J., & Zou, R. (2015). Lanthanide contraction effects on the structures, thermostabilities, and CO2 adsorption and separation behaviors of isostructural lanthanide-organic frameworks. CrystEngCommunity, 17(7), 1637-1645. DOI: 10.1039/C4CE02073A

Nakai, H., Goto, T., Kitagawa, K., Nonaka, K., Matsumoto, T., & Ogo, S. (2014). A highly luminescent and highly oxygen-sensitive Tb(III) complex with a tris-aryloxide functionalised 1,4,7 triazacyclononane ligand. Chemical Communications, 50, 15737-15739. DOI: 10.1039/C4CC07717B

Okamoto, Y. (2002). Organo lanthanide metal complexes for electroluminescent materials. Chemical Reviews, 102(6), 2357-2368. DOI: 10.1021/cr010448y

Regueiro-Figueroa, M., Esteban-Gómez, D., de Blas, A., Rodríguez-Blas, T., & Platas-Iglesias, C. (2014). Understanding stability trends along the lanthanide series. Chemistry – A European Journal, 20(14), 3974-3981. DOI: 10.1002/chem.201304469

Sastri, V. S., Bünzli, J.-C. G., Rao, V. R., Rayudu, G. V. S., & Perumareddi, J. R. (2003). In Modern Aspects of Rare Earth and Their Complexes. New York, USA: Elsevier.

Seidel, C., Lorbeer, C., Cybińska, J., Mudring, A. V., & Ruschewitz, U. (2012). Lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand: thermal and optical properties. Inorganic Chemistry, 51(8), 4679-4688. DOI: 10.1021/ic202655d

Sheldrick, G. M. (2015). Crystal structure refinement with SHELXL. Acta Crystallographica Section C: Crystal Structure Communications, C71, 3-8. DOI:10.1107/S2053229614024218

Sheu, H. S., Shih, W. J., Chuang, W. T., Li, I. F., & Yeh, C. S. (2010). Crystal structure and phase transitions of Gd(CO3)OH studied by synchrotron powder diffraction. Journal of the Chinese Chemical Society, 57(4B), 938-945. DOI: 10.1002/jccs.201000130

Sivakumar, S., Reddy, M. L. P., Cowley, A. H., & Butorac, R. R. (2011). Lanthanide-based coordination polymers assembled from derivatives of 3,5-dihydroxy benzoates: syntheses, crystal structures, and photophysical properties. Inorganic Chemistry, 50(11), 4882-4891. DOI: 10.1021/ic2001249

Sun, J., Kyotani, T., & Tomita, A. (1986). Preparation and characterization of lanthanum carbonate hydroxide. Journal of Solid State Chemistry, 65(1), 94-99. DOI: 10.1016/0022-4596(86)90093-9

Wang, C. G., Xing, Y. H., Li, Z. P., Li, J., Zeng, X. Q., Ge, M. F., & Niu, S. Y. (2009). A series of three-dimensional lanthanide-rigid-flexible frameworks: synthesis, structure, and luminescent properties of coordination polymers with 2,5-pyridine dicarboxylic acid and adipic acid. Crystal Growth and Design, 9(3), 1525-1530. DOI: 10.1021/cg801157k

Xu, Y., Ding, S. H., Feng, W. J., Zhou, G. P., & Liu, Y. G. (2006). Samarium(III) carbonate hydroxide. Acta Crystallographica Section E: Structure Reports Online, E62, i147-i149. DOI: 10.1107/S1600536806022665

Xu, W., Zhou, Y., Huang, D., Xiong, W., Su, M., Wang, K., Han, S., & Hong, M. (2013). Crystal structure, multiplex photoluminescence, and magnetic properties of a series of lanthanide coordination polymers based on quinoline carboxylate ligand. Crystal Growth and Design, 13(13), 5420-5432. DOI: 10.1021/cg401391b

Yan, X., Li, Y., Wang, Q., Huang, X., Zhang, Y., Gao, C., . . . Shao, Y. (2011). Two- to one-dimensional: radii-dependent self-assembly crystal structures and luminescent properties of lanthanide coordination polymers with an amide type semirigid bridging ligand. Crystal Growth and Design, 11(9), 4205-4212. DOI: 10.1021/cg200816f

Zhang, J., Zheng, B., Zhao, T., Li, G., Huo, Q., & Liu, Y. (2014). Topological diversities and luminescent properties of lanthanide metal-organic frameworks based on a tetracarboxylate ligand. Crystal Growth and Design, 14(5), 2394-2400. DOI: 10.1021/cg500114k

Zhang, Y., Huang, L., Miao, H., Wan, H. X., Mei, H., Liu, Y., & Xu, Y. (2015). Hydrothermal synthesis, structure, and optical properties of two nanosized Ln26@CO3 (Ln = Dy and Tb) cluster-based lanthanide-transition-metal-organic frameworks (Ln MOFs). Chemistry – A European Journal, 21(8), 3234-3241. DOI: 10.1002/chem.201405178

Zhao, B., Chen, X. Y., Cheng, P., Liao, D. Z., Yan, S. P., & Jiang, Z. H. (2004). Coordination polymers containing 1D channels as selective luminescent probes. Journal of the American Chemical Society, 126(47), 15394-15395. DOI: 10.1021/ja047141b




How to Cite

Phailyn Khemthong, Filip Kielar, & Kittipong Chainok. (2023). Solvothermal synthesis, structure, and luminescent properties of a series of 3D lanthanide carbonate frameworks. Journal of Current Science and Technology, 6(1), 97–107. Retrieved from



Research Article