Jump to ContentJump to Main Navigation
Show Summary Details

Chemical Papers

IMPACT FACTOR 2015: 1.326

SCImago Journal Rank (SJR) 2015: 0.382
Source Normalized Impact per Paper (SNIP) 2015: 0.560
Impact per Publication (IPP) 2015: 1.279

See all formats and pricing
Volume 68, Issue 2 (Feb 2014)


Synthesis and photophysical properties of new Ln(III) (Ln = Eu(III), Gd(III), or Tb(III)) complexes of 1-amidino-O-methylurea

L. Singh
  • Department of Chemistry, Manipur University, Imphal, Manipur, 795 003, India
  • Email:
/ R. Singh
  • Department of Chemistry, Manipur University, Imphal, Manipur, 795 003, India
  • Email:
Published Online: 2013-10-30 | DOI: https://doi.org/10.2478/s11696-013-0446-1


Three new solid lanthanide(III) complexes, [Ln(1-AMUH)3] · (NO3)3 (1-AMUH = 1-amidino-O-methylurea; Ln = Eu(III), Gd(III), or Tb(III)) were synthesised and characterised by elemental analysis, infrared spectra, magnetic moment measurement, and electron paramagnetic resonance (EPR) spectra for Gd(III) complex. The formation of lanthanide(III) complexes is confirmed by the spectroscopic studies. The photophysical properties of Gd(III), Eu(III), and Tb(III) complexes in solid state were investigated. The Tb(III) complex exhibits the strongest green emission at 543 nm and the Eu(III) complex shows a red emission at 615 nm while the Gd(III) complex shows a weak emission band at 303 nm. Under excitation with UV light, these complexes exhibited an emission characteristic of central metal ions. The powder EPR spectrum of the Gd(III) complex at 300 K exhibits a single broad band with g = 2.025. The bi-exponential nature of the decay lifetime curve is observed in the Eu(III) and Tb(III) complexes. The results reveal them to have potential as luminescent materials.

Keywords: lanthanide complexes; luminescence; decay lifetime; 1-amidino-O-methylurea

  • [1] Agarwal, R. K., & Gupta, S. K. (1987). Spectral and thermal investigations in lanthanum(III) and lanthanide (III) complexes of 5,6-benzoquinoline. Polish Journal of Chemistry, 61, 341–354.

  • [2] Aime, S., Botta, M., Fasano, M., Crich, S. G., & Terreno, E. (1996). Gd(III) complexes as contrast agents for magnetic resonance imaging: a proton relaxation enhancement study of the interaction with human serum albumin. Journal of Biological Inorganic Chemistry, 1, 312–319. DOI: 10.1007/s007750050059. http://dx.doi.org/10.1007/s007750050059 [Crossref]

  • [3] Binnemans, K. (2009). Lanthanide-based luminescent hybrid materials. Chemical Reviews, 109, 4283–4374. DOI: 10.1021/cr8003983. http://dx.doi.org/10.1021/cr8003983 [Web of Science] [Crossref]

  • [4] Binnemans, K., & Görller-Walrand, C. (2002). Lanthanidecontaining liquid crystals and surfactants. Chemical Reviews, 102, 2303–2345. DOI: 10.1021/cr010287y. http://dx.doi.org/10.1021/cr010287y [Crossref]

  • [5] Bünzli, J. C. G., & Piguet, C. (2002). Lanthanide-containing molecular and supramolecular polymetalic functional assemblies. Chemical Reviews, 102, 1897–1928. DOI: 10.1021/cr010299j. http://dx.doi.org/10.1021/cr010299j [Crossref]

  • [6] Bünzli, J. C. G., Chauvin, A. S., Kim, H. K., Deiters, E., & Eliseeva, S. V. (2010). Lanthanide luminescence efficiency in eight- and nine-coordinate complexes: Role of the radiative lifetime. Coordination Chemistry Reviews, 254, 2623–2633. DOI: 10.1016/j.ccr.2010.04.002. http://dx.doi.org/10.1016/j.ccr.2010.04.002 [Web of Science] [Crossref]

  • [7] Costes, J. P., Clemente-Juan, J. M., Dahan, F., Nicodème, F., & Verelst, M. (2002). Unprecedented ferromagnetic interaction in homobinuclear erbium and gadolinium complexes: Structural and magnetic studies. Angewandte Chemie International Edition, 41, 323–325. DOI: 10.1002/1521-3773(20020118)41:2<323. http://dx.doi.org/10.1002/1521-3773(20020118)41:2<323::AID-ANIE323>3.0.CO;2-9 [Crossref]

  • [8] Devi, S. P., Singh, R. K. H., & Kadam, R. M. (2006). Synthesis and spectroscopic studies on copper(II) binuclear complexe of 1-phenylamidino-O-alkylurea (alkyl = n-propyl, n- and iso-butyl) with 1,3-diaminopropane or ethylenediamine. Inorganic Chemistry, 45, 2193–2198. DOI: 10.1021/ic051037t. http://dx.doi.org/10.1021/ic051037t [Crossref]

  • [9] Forsberg, J. H., & Moeller, T. (1969). Rare earths. LXXIX. Syntheses and properties of ethylenediamine chelates of the tripositive lanthanide ions. Inorganic Chemistry, 8, 883–888. DOI: 10.1021/ic50074a036. http://dx.doi.org/10.1021/ic50074a036 [Crossref]

  • [10] Gudasi, K. B., Shenoy, R. V., Vadavi, R. S., Patil, M. S., Patil, S. A., Hanchinal, R. R., Desai, S. A., & Lohithaswa, H. (2006). Lanthanide(III) and yttrium(III) complexes of benzimidazole-2-acetic acid: Synthesis, characterization and effect of La(III) complex on germination of wheat. Bioinorganic Chemistry and Applications, 2006, 75612. DOI: 10.1155/bca/2006/75612. [Crossref]

  • [11] Gusev, A. N., Shul’gin, V. F., Nishimenko, G., Hasegawa, M., & Linert, W. (2013). Photo- and electroluminescent properties europium complexes using bistriazole ligands. Synthetic Metals, 164, 17–21. DOI: 10.1016/j.synthmet.2012.12.020. http://dx.doi.org/10.1016/j.synthmet.2012.12.020 [Crossref]

  • [12] Hirashima, Y., Kanetsuki, K., Yonezu, I., Kamakura, K., & Shiokawa, J. (1983). Lanthanoid nitrate complexes with some polyethylene glycols and glymes. Bulletin of the Chemical Society of Japan, 56, 738–743. DOI: 10.1246/bcsj.56.738. http://dx.doi.org/10.1246/bcsj.56.738 [Crossref] [Web of Science]

  • [13] Huang, H. L., Zhong, C. F., Zhang, H. L., & Zhou, Y. (2008). Synthesis and photophysical properties of novel polymeric Eu(III) complex with bicoordination ligand. Journal of Luminescence, 128, 1863–1866. DOI: 10.1016/j.jlumin.2008.05.008. http://dx.doi.org/10.1016/j.jlumin.2008.05.008 [Crossref]

  • [14] Hughes, E. W. (1940). The crystal structure of dicyandiamide. Journal of the American Chemical Society, 62, 1258–1267. DOI: 10.1021/ja01862a079. http://dx.doi.org/10.1021/ja01862a079 [Crossref]

  • [15] Hughes, E. W. (1940). Contribution from the Gates and Crellin Laboratories of Chemistry, 62, 1258.

  • [16] Kido, J., & Okamoto, Y. (2002). Organo lanthanide metal complexes for electroluminescent materials. Chemical Reviews, 102, 2357–2368. DOI: 10.1021/cr010448y. http://dx.doi.org/10.1021/cr010448y [Crossref]

  • [17] Loitongbam, R. S., Singh, W. R., Phaomei, G., & Singh, N. S. (2013). Blue and green emission from Ce3+ and Tb3+ codoped Y2O3 nanoparticles. Journal of Luminescence, 140, 95–102. DOI: 10.1016/j.jlumin.2013.02.049. http://dx.doi.org/10.1016/j.jlumin.2013.02.049 [Web of Science] [Crossref]

  • [18] Mahajan, R. K., Kaur, I., Kaur, R., Onimaru, A., Shinoda, S., & Tsukube, H. (2004). Lipophilic lanthanide tris(β-diketonate) complexes as an ionophore for Cl− anionselective electrodes. Analytical Chemistry, 76, 7354–7359. DOI: 10.1021/ac0497858. http://dx.doi.org/10.1021/ac0497858 [Crossref]

  • [19] McDonald, J. E., & Moeller, T. (1977). The rare earths-XC. Lanthanide(III) complexes of 1,3-propanediamine. Journal of Inorganic and Nuclear Chemistry, 39, 2287–2288. DOI: 10.1016/0022-1902(77)80416-8. http://dx.doi.org/10.1016/0022-1902(77)80416-8 [Crossref]

  • [20] Moeller, T., Birnbaum, E. R., Forsberg, J. H., & Gayhart, R. B. (1968). Some aspects of the coordination chemistry of the rare earth. In L. Eyring (Ed.), Progress in the science and technology of the rare earths (Vol. 3, pp. 66–128). New York, NY, USA: Pergamon Press.

  • [21] Moeller, T., Martin, D. F., Thompson, L. C., Ferrús, R., Feistel, G. R., & Randall, W. J. (1965). The coordination chemistry of yttrium and rare earth metal ions. Chemical Reviews, 65, 1–50. DOI: 10.1021/cr60233a001. http://dx.doi.org/10.1021/cr60233a001 [Crossref]

  • [22] Mutalik, V., & Phaniband, M. A. (2011). Synthesis, characterization, fluorescent and antimicrobial properties of new lanthanide(III) complexes derived from coumarin Schiff base. Journal of Chemical and Pharmaceutical Research, 3, 313–330.

  • [23] Mungchamnakit, A., Limsuwan, P., Thongcham, K., & Meejoo, S. (2008). The electron spin resonance study of Gd3+ in natural zircon. Journal of Magnetism and Magnetic Materials, 320, 479–482. DOI: 10.1016/j.jmmm.2007.07.014. http://dx.doi.org/10.1016/j.jmmm.2007.07.014 [Crossref]

  • [24] Nakamoto, K. (1986). Infrared and Raman spectra of inorganic and coordination compounds (4th ed., pp. 257). New York, NY, USA: Wiley.

  • [25] Ndao, A. S., Buzády, A., Erostyák, J., & Hornyák, I. (2008). Sensitized luminescence of trivalent lanthanide complexes Eu3+/quinaldinic acid and Eu3+/1,4-dihydro-oxo-chinoline-3-carboxylic acid. Journal of Fluorescence, 18, 649–654. DOI: 10.1007/s10895-008-0333-2. http://dx.doi.org/10.1007/s10895-008-0333-2 [Crossref] [Web of Science]

  • [26] Prasad, S., Agarwal, R. K., & Kumar, A. (2011). Synthesis, characterization and biological evaluation of a novel series of mixed ligand complexes of lanthanides(III) with 4[N-(furfural)amino]antipyrine semicarbazone as primary ligand and diphenyl sulfoxide as secondary ligand. Journal of the Iranian Chemical Society, 8, 825–839. DOI: 10.1007/bf03245913. http://dx.doi.org/10.1007/BF03245913 [Web of Science] [Crossref]

  • [27] Ramirez, F. D. M., Sosa-Torres, M. L., Castro, M., Basurto-Uribe, E., Zamorano-Ulloa, R., & del Río-Portilla, F. (1997). Synthesis, 1H, 13C NMR and magnetic studies of the homodinuclear lanthanide(III) polymeric compounds formed with the 1,5,9,13-tetraazacyclonehexadecane ligand. Journal of Coordination Chemistry, 41, 303–326. DOI: 10.1080/00958979708045507. http://dx.doi.org/10.1080/00958979708045507 [Crossref]

  • [28] Radhakrisnan, P. K., Indrasenan, P., & Nair, C. G. R. (1984). Complexes of lanthanide nitrates with 4n-(2′-hydroxybenzylidene)-aminoantipyrine. Polyhedron, 3, 67–70. DOI: 10.1016/s0277-5387(00)84714-2. http://dx.doi.org/10.1016/S0277-5387(00)84714-2

  • [29] Rizzi, A., Baggio, R., Calvo, R., Garland, M. T., Peña, O., & Perec, M. (2001). Synthesis, crystal structure and magnetic properties of the mixed-ligand complex [Gd(CF3CO2)3 (phen)2(H2O)]. Inorganic Chemistry, 40, 3623–3625. DOI: 10.1021/ic001243v. http://dx.doi.org/10.1021/ic001243v [Crossref]

  • [30] Singh, L. J., Devi, N. S., Devi, S. P., Devi, W. B., Singh, R. K. H., Rajeswari, B., & Kadam, R. M. (2010). Spectroscopic studies on bis(1-amidino-O-alkylurea) copper(II) sulphate complexes where alkyl = methyl, ethyl, n-propyl or n-butyl: EPR evidence for binuclear complexes. Inorganic Chemistry Communications, 13, 365–368. DOI:10.1016/j.inoche.2009.12.023. http://dx.doi.org/10.1016/j.inoche.2009.12.023 [Crossref]

  • [31] Singh, L. J., Singh, R. K. H., & Chitra, R. (2012). Synthesis, spectroscopic, powder X-ray diffraction and DNA binding studies on copper(II) complexes of 4,4′-diaminodiphenyl sulfone. Journal of the Iranian Chemistry Society, 9, 441–448. DOI: 10.1007/s13738-011-0054-3. http://dx.doi.org/10.1007/s13738-011-0054-3 [Web of Science] [Crossref]

  • [32] Svatos, G. F., Curran, C., & Quagliano, J. V. (1955). Infrared absorption spectra of inorganic coordination complexes.1a,b V. The N-H stretching vibration in coordination compounds. Journal of the American Chemical Society, 77, 6159–6163. DOI: 10.1021/ja01628a019. http://dx.doi.org/10.1021/ja01628a019 [Crossref]

  • [33] Wang, H. D., Chen, Y., Li, Y. T., & Zeng, X. C. (2004). Synthesis, characterisation, and thermal decomposition of oxamido heterobinuclear Cu(II)-Ln(III) complexes. Thermochimica Acta, 412, 97–105. DOI: 10.1016/j.tca.2003.09.006. http://dx.doi.org/10.1016/j.tca.2003.09.006 [Crossref]

  • [34] Wu, A. Q., Zheng, F. K., Chen, W. T., Cai, L. Z., Guo, G. C., Huang, J. S., Dong, Z. C., & Takano, Y. (2004). Two series of novel rare earth complexes with dicyanamide [Ln(dca)2(phen)2(H2O)3][dca]·(phen), (Ln = Pr, Gd, and Sm) and [Ln(dca)3(2,2′-bipy)2(H2O)]n, (Ln = Gd, Sm, and La): Syntheses, crystal structures, and magnetic properties. Inorganic Chemistry, 43, 4839–4845. DOI: 10.1021/ic035470j. http://dx.doi.org/10.1021/ic035470j [Crossref]

  • [35] Yan, B., & Song, Y. S. (2004). Spectroscopic study on the photophysical properties of lanthanide complexes with 2,2′-bipyridine-N,N′-dioxide. Journal of Fluorescence, 14, 289–294. DOI: 10.1023/b:jofl.0000024561.55183.26. http://dx.doi.org/10.1023/B:JOFL.0000024561.55183.26 [Crossref]

  • [36] Zucchi, G. (2011). The utility of 2,2′-bipyridine in lanthanide chemistry: From materials synthesis to structural and physical properties. International Journal of Inorganic Chemistry, 2011, 918435. DOI: 10.1155/2011/918435. http://dx.doi.org/10.1155/2011/918435 [Crossref]

About the article

Published Online: 2013-10-30

Published in Print: 2014-02-01

Citation Information: Chemical Papers, ISSN (Online) 1336-9075, DOI: https://doi.org/10.2478/s11696-013-0446-1. Export Citation

Citing Articles

Here you can find all Crossref-listed publications in which this article is cited. If you would like to receive automatic email messages as soon as this article is cited in other publications, simply activate the “Citation Alert” on the top of this page.

Zheng Li, Jing-Jian Zhou, Si-Yu Zuo, Xiao Yuan, Chen-Chen Ma, Yi-Shan Song, and Hua Zhang
Chemical Papers, 2015, Volume 0, Number 0

Comments (0)

Please log in or register to comment.
Log in