Synthesis, structure, reactivity and photoluminescence of lanthanide(III) monoporphyrinate complexes

Rick W K WONG*, Xunjin ZHU, Wai Yeung WONG

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

122 Citations (Scopus)


A series of cationic lanthanide(III) monoporphyrinate complexes of the general formula [Ln(Por)(H2O)3]Cl (Ln = Yb3+ and Er3+; Por = porphyrinate dianion) were prepared via the protonolysis of Ln(NR2)3 with porphyrin free bases (H2Por). An unexpected neutral oxalate-bridged Yb porphyrinate dimer [Yb(Por)(DME)]2(μ-η22-O2CCO2) was isolated and structurally characterized by X-ray crystallography when the protonolysis was carried out in an atmosphere of carbon dioxide. The coordinated aqua molecules of the cationic porphyrinate complexes are very labile and can be easily displaced by good donor solvents such as DMF or anionic tripodal ligand L2X- (L2X- = LOMe- and TpH-) to form the neutral complex [Ln(Por)(Cl)(DMF)2] or [Ln(Por)(L2X)], respectively. [Yb(Por)(H2O)3]Cl underwent dimerization to give the dimer [Yb(Por)(μ-OH)(H2O)]2 when dissolved in basic solution and [Yb(Por)(μ-Cl)(H2O)]2 in dilute HCl solution. Furthermore, [Yb(Por)(H2O)3]Cl behaves as a living catalyst for the cyclotrimerization of phenyl isocyanate to l,3,5-triphenyl-s-triazin-2,4,6-trione. Photoluminescence studies showed that the porphyrinate dianion, acting as an antenna, sensitized Ln3+ (Ln3+ = Nd3+, Er3+ and Yb3) ion emission in the near-infrared region, and that [Ln(TDPAPP)(LOMe)] complexes exhibited excellent optical limiting capability. Protonolysis of Ln(NR2)3 with N-confused porphyrin free bases (H2NCP) followed by the addition of the encapsulating tripodal anion, LOMe, gave lanthanide(III) N-confused porphyrinate complexes of the general formula [Ln(NCP)(LOMe)] (Ln = Yb3+ and Er3+; NCP = N-confused porphyrinate dianion), whose X-ray structures revealed an η2 agostic interaction between the metal center and the inner C-H bond of the NCP ligand.

Original languageEnglish
Pages (from-to)2386-2399
Number of pages14
JournalCoordination Chemistry Reviews
Issue number17-20
Publication statusPublished - Sept 2007

Scopus Subject Areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

User-Defined Keywords

  • Cationic lanthanide monoporphyrinate complexes
  • Lanthanide porphyrinate dimers
  • Metal-catalyzed cyclotrimerization
  • N-Confused porphyrin
  • Near-infrared sensitization
  • Optical limiting property


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