Synthetic, structural, spectroscopic, and electrochemical studies, of heteroleptic tris(phthalocyaninato) rare earth complexes

Yongzhong Bian, Lei Li, Daqi Wang, Chi Fung Choi, Diana Y.Y. Cheng, Pehua Zhu, Renjie Li, Jianmin Dou, Rongming Wang, Na Pan, Dennis K.P. Ng, Nagao Kobayashi, Jianzhuang Jiang

Research output: Contribution to journalArticlepeer-review

44 Citations (Scopus)

Abstract

Three heteroleptic tris(phthalocyaninato) rare-earth triple-decker complexes [(Pc)M(Pc)M{Pc(α-OC5H11)4}] [M = Sm, Gd, Lu; Pc = phthalocyaninate; Pc(α-OC5H 11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate] have been prepared as racemic mixtures by treating [M{Pc(α-OC 5H11)4}(acac)], generated in situ, with the bis(phthalocyaninato) rare-earth double-decker complex [M(Pc)2] in refluxing n-octanol. The molecular structures of the gadolinium and lutetium complexes have been determined by single-crystal X-ray diffraction analysis, both of which adopt the asymmetrical structure [(Pc)M(Pc)M{Pc(α-OC 5H11)4}]. The outer Pc and Pc(α-OC 5H11)4 rings are significantly domed, while the inner Pc ring is essentially planar. The ring-to-ring separation between the two adjacent Pc rings, as defined by the two N4 mean planes, diminishes from [(Pc)Gd(Pc)Gd{Pc(α-OC5H11) 4}] to [(Pc)Lu(Pc)Lu{Pc(α-OC5H11) 4}] as a result of the smaller LuIII ion. The decreased molecular symmetry for these complexes has also been revealed by the NMR spectra of the samarium and lutetium analogs, in which four sets of signals appear for the inner Pc ring protons due to the special disposition of the neighboring Pc(α-OC5H11)4 ring. Electrochemical studies have revealed four one-electron oxidations and up to five one-electron reductions for these complexes. The dependence of the phthalocyanine Q band as well as the first and second oxidation potentials on the size of the metal center indicates that substantial π-π interactions are present in these compounds.

Original languageEnglish
Pages (from-to)2612-2618
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Issue number13
DOIs
Publication statusPublished - 2005 Jul 4

Keywords

  • Heteroleptic complexes
  • Phthalocyanines
  • Rare earths
  • Sandwich complexes
  • Triple-decker complexes

ASJC Scopus subject areas

  • Inorganic Chemistry

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