Ferrocene-decorated (phthalocyaninato)(porphyrinato) double- and triple-decker rare earth complexes: Synthesis, structure, and electrochemical properties

Peihua Zhu, Xiuwen Zhang, Hailong Wang, Yuexing Zhang, Yongzhong Bian*, Jianzhuang Jiang

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

Abstract

A series of four mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes (Pc)M[Por(Fc) 2] [Pc = phthalocyaninate; Por(Fc) 2 = 5,15-di(ferrocenyl)-porphyrinate; M = Eu (1), Y (2), Ho (3), Lu (4)] and their europium(III) triple-decker counterpart (Pc)Eu(Pc)Eu[Por(Fc) 2] (5), each with two ferrocenyl units at the meso-positions of their porphyrin ligands, have been designed and prepared. The double- and triple-decker complexes 1-5 were characterized by elemental analysis and various spectroscopic methods. The molecular structures of two double-deckers 1 and 4 were also determined by single-crystal X-ray diffraction analysis. Electrochemical studies of these novel sandwich complexes revealed two consecutive ferrocene-based one-electron oxidation waves, suggesting the effective electronic coupling between the two ferrocenyl units. Nevertheless, the separation between the two consecutive ferrocene-based oxidation waves increases from 1 to 4, along with the decrease of rare earth ionic radius, indicating the effect of rare earth size on tuning the coupling between the two ferrocenyl units. Furthermore, the splitting between the two ferrocene-based one-electron oxidations for triple-decker 5 is even smaller than that for 1, showing that the electronic interaction between the two ferrocene centers can also be tuned through changing the linking sandwich framework from double-decker to triple-decker. For further understanding of the electronic coupling between ferrocenyl groups, DFT calculation is carried out to clarify the electronic delocalization and the molecular orbital distribution in these double-decker complexes.

Original languageEnglish (US)
Pages (from-to)5651-5659
Number of pages9
JournalInorganic Chemistry
Volume51
Issue number10
DOIs
StatePublished - May 21 2012

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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