Organometallic complexes for nonlinear optics: Part 31. Cubic hyperpolarizabilities of ferrocenyl-linked gold and ruthenium complexes

Stephanie K. Hurst, Mark G. Humphrey, Joseph P. Morrall, Marie P. Cifuentes, Marek Samoc, Barry Luther-Davies, Graham A. Heath, Anthony C. Willis

Research output: Contribution to journalArticle

60 Scopus citations

Abstract

The complexes [Fe{η-C 5 H 4 -(E)-CH= CH-4-C 6 H 4 C≡CX} 2 ] [X=SiMe 3 (1), H (2), Au(PCy 3 ) (3), Au(PPh 3 ) (4), Au(PMe 3 ) (5), RuCl(dppm) 2 (7), RuCl(dppe) 2 (8)] and [Fe{η-C 5 H 4 -(E)-CH= CH-4-C 6 H 4 CH≡CRuCl} (dppm) 2 } 2 ](PF 6 ) 2 (6) have been prepared and the identities of 1 and 7 confirmed by single-crystal X-ray structural studies. Complexes 1-8 exhibit reversible oxidation waves in their cyclic voltammograms attributed to the Fe II/III couple of the ferrocenyl groups, 6-8 also showing reversible (7, 8) or nonreversible (6) processes attributed to Ru-centered oxidation. Cubic nonlinearities at 800 nm by the Z-scan method are low for 1-5; in contrast, complexes 6 and 7 exhibit large negative γ real and large γ imag values. A factor of 4 difference in γ and two-photon absorption cross-section σ 2 values for 6 and 7 suggest that they have potential as protically switchable NLO materials.

Original languageEnglish (US)
Pages (from-to)56-65
Number of pages10
JournalJournal of Organometallic Chemistry
Volume670
Issue number1-2
DOIs
StatePublished - Mar 17 2003
Externally publishedYes

Keywords

  • Acetylide
  • Electrochemistry
  • Gold
  • Hyperpolarizability
  • Iron
  • Nonlinear optics
  • Ruthenium

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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