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

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journal

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Author(s)

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

Detail(s)

Original languageEnglish
Pages (from-to)1475-1485
Journal / PublicationChemistry - A European Journal
Volume12
Issue number5
Publication statusPublished - 1 Feb 2006
Externally publishedYes

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. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Research Area(s)

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

Citation Format(s)

Controlling the nature of mixed (phthalocyaninato)(porphyrinato) rare-earth(III) double-decker complexes : The effects of nonperipheral alkoxy substitution of the phthalocyanine ligand. / Wang, Rongming; Li, Renjie; Li, Yong; Zhang, Xianxi; Zhu, Peihua; Lo, Pui-Chi; Ng, Dennis K. P.; Pan, Na; Ma, Changqin; Kobayashi, Nagao; Jiang, Jianzhuang.

In: Chemistry - A European Journal, Vol. 12, No. 5, 01.02.2006, p. 1475-1485.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journal