Optical, magnetic, and electronic properties of peripherally fused macrocycles: Molybdocene porphyrazines

K. Deng, Z. Ding, D. E. Ellis*, S. L.J. Michel, B. M. Hoffman

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations


Metal-free and copper porphyrazines, [H2pz] and [Cu pz], have been fused at the periphery with molybdocene dithiolene, [Cp2Mo]. The optical, magnetic, and electronic properties of the resulting neutral and cationic complexes are studied, using first-principles density functional theory implemented by the discrete variational method. Analysis of the charge and spin distribution shows that the porphyrazine core is strongly coupled with the peripheral complex. The calculated optical absorption is found to be in reasonable agreement with experimental spectra, lending support to our theoretical model. Under appropriate circumstances one observes interaction of unpaired spins localized in the vicinity of both metal sites. The calculated spin distribution shows that [Cp2Mo][Cu pz] and [Cp2Mo][H2pz]+ have a magnetic moment of 1 μB while [Cp2Mo][Cu pz]+ and [Cp2Mo][H2pz] have no moment, in good agreement with the results of X-band EPR spectra. The Cu-Mo magnetic interaction is antiferromagnetic, being mediated by pyrrol nitrogens, meso nitrogens, carbons, and sulfurs.

Original languageEnglish (US)
Pages (from-to)1110-1115
Number of pages6
JournalInorganic chemistry
Issue number6
StatePublished - Mar 12 2001

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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