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Synthesis, Structure and Spectroscopic Properties of Lanthanide Complexes of N-Confused Porphyrins

  1. Xun-Jin Zhu,
  2. Feng-Lei Jiang,
  3. Chun-Ting Poon,
  4. Wai-Kwok Wong,
  5. Wai-Yeung Wong

Article first published online: 10 JUN 2008

DOI: 10.1002/ejic.200800267

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Volume 2008, Issue 20, pages 3151–3162, July 2008

Additional Information

How to Cite

Zhu, X.-J., Jiang, F.-L., Poon, C.-T., Wong, W.-K. and Wong, W.-Y. (2008), Synthesis, Structure and Spectroscopic Properties of Lanthanide Complexes of N-Confused Porphyrins. Eur. J. Inorg. Chem., 2008: 3151–3162. doi: 10.1002/ejic.200800267

Author Information

  1. Department of Chemistry and Center for Advanced Luminescence Materials, Hong Kong Baptist University, Kowloon Tong, Hong Kong, P. R. China, Fax: +852-3411-5862

Publication History

  1. Issue published online: 10 JUL 2008
  2. Article first published online: 10 JUN 2008
  3. Manuscript Received: 13 MAR 2008

Funded by

  • Hong Kong Baptist University. Grant Numbers: FRG/05-06/I-12, FRG/05-06/II-03
  • Hong Kong Research Grants Council. Grant Number: HKBU 2021/03P

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Keywords:

  • N ligands;
  • Lanthanides;
  • Porphyrinoids;
  • Agostic interactions;
  • Fluo­res­cence

Abstract

A series of meso-substituted N-confused porphyrins (NCP) is synthesized using the modified Rothemund–Lindsey procedure. Lanthanide N-confused porphyrinate complexes of the general formula [(NCP)Ln(LOMe)] [Ln3+ = Yb3+ and Er3+; Lmath image = (η5-C5H5)Co{P(=O)(OMe)2}3–] are obtained in moderate yields upon interaction of N-confused porphyrin free bases (H2NCP) with Ln[N(SiMe2)3]·x[LiCl(THF)3], followed by the addition of the tripodal anion Lmath image as an effective encapsulating agent for the lanthanide ions. The structural and spectroscopic data for these complexes provide evidence for an η2-agostic interaction between the Ln3+ ion and the inner C–H bond of the NCP ligand. Methylation of [(NCTCPP)Yb(LOMe)] (H2NCTCPP = 2-azo-5,10,15,20-tetracyanophenyl-21-carbaporphyrin) with methyl iodide yields the novel stable lanthanide complex of the N-methylated derivative of N-confused porphyrins, whose X-ray structure also exhibits an η2-agostic interaction between the metal center and the inner C–H bond of the NCTCPP ligand. The photophysical properties of the N-confused porphyrins and their lanthanide complexes are investigated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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