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Experimental and Theoretical Approaches Toward Anion-Responsive Tripod–Lanthanide Complexes: Mixed-Donor Ligand Effects on Lanthanide Complexation and Luminescence Sensing Profiles

  1. Yumiko Kataoka Dr.1,
  2. Dharam Paul Dr.1,
  3. Hiroyuki Miyake Dr.1,
  4. Tsuyoshi Yaita Dr.2,
  5. Eisaku Miyoshi Prof.3,
  6. Hirotoshi Mori Dr.3,
  7. Shinya Tsukamoto3,
  8. Hiroshi Tatewaki Prof.4,
  9. Satoshi Shinoda Dr.1,
  10. Hiroshi Tsukube Prof.1

Article first published online: 30 APR 2008

DOI: 10.1002/chem.200701898

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 14, Issue 17, pages 5258–5266, June 9, 2008

Additional Information

How to Cite

Kataoka, Y., Paul, D., Miyake, H., Yaita, T., Miyoshi, E., Mori, H., Tsukamoto, S., Tatewaki, H., Shinoda, S. and Tsukube, H. (2008), Experimental and Theoretical Approaches Toward Anion-Responsive Tripod–Lanthanide Complexes: Mixed-Donor Ligand Effects on Lanthanide Complexation and Luminescence Sensing Profiles. Chem. Eur. J., 14: 5258–5266. doi: 10.1002/chem.200701898

Author Information

  1. 1

    Department of Chemistry, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan, Fax: (+81) 6-6605-2560

  2. 2

    Actinide Coordination Chemistry Group, Synchrotron Radiation Research Center, Quantum Beam Science Directorate, Japan Atomic Energy Agency, 1-1-1 Koto, Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan

  3. 3

    Graduate School of Engineering Science, Kyushu University, 6-1 Kasuga-Park, Fukuoka 816-8580, Japan

  4. 4

    Department of Information and Biological Sciences, Graduate School of Natural Sciences, Nagoya City University, 1 Yamanohata, Mizuho-cho, Mizuho-ku, Nagoya, Aichi 467-8501, Japan

Publication History

  1. Issue published online: 29 MAY 2008
  2. Article first published online: 30 APR 2008
  3. Manuscript Received: 3 DEC 2007

Funded by

  • The Ministry of Education, Culture, Sports, Science, and Technology (Japan). Grant Numbers: 16080217, 17350030

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Keywords:

  • anion sensing;
  • density functional calculations;
  • EXAFS spectroscopy;
  • lanthanides;
  • luminescence

Abstract

A new series of tripods were designed to form anion-responsive, luminescent lanthanide complexes. These tripods contain pyridine, thiazole, pyrazine, or quinoline chromophores combined with amide carbonyl oxygen and tertiary nitrogen atoms. Crystallographic and EXAFS studies of the 10-coordinated tripod–La(NO3)3 complexes revealed that each La3+ cation was cooperatively coordinated by one tetradentate tripod and three bidentate NO3− anions in the crystal and in CH3CN. Quantum chemical calculations indicated that the aromatic nitrogen plays a significant role in lanthanide complexation. The experimentally determined stability constants of complexes of the tripod with La(NO3)3, Eu(NO3)3, and Tb(NO3)3 were in good agreement with the theoretically calculated interaction energies. Complexation of each tripod with lanthanide triflate gave a mixture of several lanthanide complex species. Interestingly, the addition of a coordinative NO3− or Cl− anion to the mixture significantly influenced the lanthanide complexation profiles. The particular combination of tripod and a luminescent Eu3+ center gave anion-selective luminescence enhancements. Pyridine-containing tripods exhibited the highest NO3− anion-selective luminescence and thus permit naked-eye detection of the NO3− anion.

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