Definitive assignments of the visible-near-IR bands of porphyrin- naphthalocyanine rare-earth sandwich double- and triple-decker compounds by magnetic circular dichroism spectroscopy

Atsuya Muranaka, Yotaro Matsumoto, Masanobu Uchiyama, Jianzhuang Jiang, Yongzhong Bian, Amout Ceulemans, Nagao Kobayashi

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20 Citations (Scopus)

Abstract

A series of heteroleptic rare-earth sandwich complexes [M(Nc)(OEP)] (M = La, Nd, Eu, Dy, and Lu; Ne = 2.3-naphthalocyaninate; OEP = octaethylporphyrinate) have been investigated by electronic absorption and magnetic circular dichroism (MCD) spectroscopy. The electronic absorption spectra of the neutral forms showed two characteristic transitions (bands I and II) in the near-IR region, both of which were systematically shifted depending on the size of their central metal. In the MCD spectra, a relatively intense Faraday A term and a significantly weak Faraday B term have been observed corresponding to bands II and I, respectively. The spectral features were successfully interpreted using a simple MO model by considering the relevant interactions of Gouterman's four orbitals of the constituent chromophores. The model succeeded in assigning the MCD spectra of the related compounds, the oxidized and reduced forms of the dimer ([M(Nc)(OEP)+ and [M(Nc)(OEP)]-), and neutral forms of the triple-decker compounds (M2(Nc)(OEP)2, M = Nd, Eu). DFT calculations of the dimers supported the validity of this model.

Original languageEnglish
Pages (from-to)3818-3826
Number of pages9
JournalInorganic Chemistry
Volume44
Issue number11
DOIs
Publication statusPublished - 2005 May 30
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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