Controlling the nature of mixed (phthalocyaninato)(porphyrinato) rare-earth(III) double-decker complexes: The effects of nonperipheral alkoxy substitution of the phthalocyanine ligand

Rongming Wang, Renjie Li, Yong Li, Xianxi Zhang, Peihua Zhu, Pui Chi Lo, Dennis K.P. Ng, Na Pan, Changqin Ma, Nagao Kobayashi, Jianzhuang Jiang

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88 Citations (Scopus)

Abstract

The half-sandwich rare-earth complexes [MIII(acac)(TClPP)] (M = Sm, Eu, Y; TClPP = meso-tetrakis (4-chlorophenyl)porphyrinate; acac = acetylacetonate), generated in situ from [M(acac)3]·n H 2O and H2(TClPP), were treated with 1,8,15,22-tetrakis(3- pentyloxy)phthalocyanine [H2{Pc(α-OC5H 11)4]} (Pc = phthalocyaninate) under reflux in n-octanol to yield both the neutral nonprotonated and protonated (phthalocyaninato) (porphyrinato) rare-earth double-decker complexes, [MIII{Pc(α- OC5H11)4}(TClPP)] (1-3) and [M IIIH{Pc(α-OC5H11)4}(TClPP)] (4-6), respectively. In contrast, reaction of [YIII(acac)(TClPP)] with 1,4,8,11,15,18,22,25-octakis(1-butyloxy)-phthalocyanine [H 2Pc(α-OC4H9)8] gave only the protonated double-decker complex [YIIIH{Pc(α-OC 4H9)8}-(TClPP)] (7). These observations clearly show the importance of the number and positions of substituents on the phthalocyanine ligand in controlling the nature of the (phthalocyaninato)- (porphyrinato) rare-earth double-deckers obtained. In particular, α-alkoxylation of the phthalocyanine ligand is found to stabilize the protonated form, a fact supported by molecular-orbital calculations. A combination of mass spectrometry, NMR, UV-visible, near-IR, MCD, and IR spectroscopy, and X-ray diffraction analyses, facilitated the differentiation of the newly prepared neutral nonprotonated and protonated double-decker complexes. The crystal structure of the protonated form has been determined for the first time.

Original languageEnglish
Pages (from-to)1475-1485
Number of pages11
JournalChemistry - A European Journal
Volume12
Issue number5
DOIs
Publication statusPublished - 2006 Feb 1

Keywords

  • Phthalocyanines
  • Porphyrinoids
  • Rare-earth elements
  • Sandwich complexes
  • Substitution effect

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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