Synthesis, structure and spectroscopic properties of lanthanide complexes of N-confused porphyrins

Xunjin ZHU, Feng Lei Jiang, Chun Ting Poon, Rick W K WONG*, Wai Yeung WONG

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

17 Citations (Scopus)

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+; LOMe- = (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(SiMe 2)3]·x[LiCl(THF)3], followed by the addition of the tripodal anion LOMe- 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.

Original languageEnglish
Pages (from-to)3151-3162
Number of pages12
JournalEuropean Journal of Inorganic Chemistry
Issue number20
DOIs
Publication statusPublished - Jul 2008

Scopus Subject Areas

  • Inorganic Chemistry

User-Defined Keywords

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

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