Organometallic complexes for nonlinear optics: Part 23. Quadratic and cubic hyperpolarizabilities of acetylide and vinylidene complexes derived from protected and free formylphenylacetylenes

Stephanie K Hurst, Nigel T. Lucas, Marie P. Cifuentes, Mark G. Humphrey, Marek Samoc, Barry Luther-Davies, Inge Asselberghs, Roel Van Boxel, André Persoons

Research output: Contribution to journalArticle

26 Scopus citations

Abstract

The acetylenes 4-HCCC6H4R [R=CH{OC(O)Me}2 (1), CHO(CH2)3O (2)], ruthenium complexes [Ru(4-CCC6H4R)(PPh3)2(η-C 5H5)] [R=CH{OC(O)Me}2 (3), CHO (4)], [Ru(n-C=CHC6H4R)Cl(dppm)2]PF6 [n=4, R=CHO(CH2)3O (7); R=CHO, n=3 (11), 2 (15)], and [Ru(n-CCC6H4R)Cl(dppm)2] [n=4, R=CHO(CH2)3O (8); n=3, R=CHO (12)], and gold complexes [Au(n-CCC6H4R)(L)] [n=4, R=CHO, L=PPh3 (5), PMe3 (6); n=4, R=CHO(CH2)3O, L=PPh3 (9), PMe3 (10); n=3, R=CHO, L=PPh3 (13), PMe3 (14)] have been prepared, and 9 characterized by a single crystal X-ray diffraction study. Electrochemical data for the ruthenium complexes reveal reversible or quasi-reversible (alkynyl complexes) or irreversible (vinylidene complexes) processes assigned to the RuII/III couple; the effect on E1/2 values of the various structural modifications across 3, 4, 7, 8, 11, 12 and 15 are discussed. The molecular quadratic and cubic optical nonlinearities of 1-15 have been determined by the hyper-Rayleigh scattering technique at 1064 nm and the Z-scan technique at 800 nm, respectively; β values increase on increasing the acceptor strength, proceeding from 3-acceptor-substituted to 4-acceptor-substituted arylalkynyl ligand, and an increasing phosphine donor strength, whereas γ values increase on increasing the number of phosphine aryl groups (i.e. increasing delocalization) proceeding from PMe3 to PPh3-containing complex.

Original languageEnglish (US)
Pages (from-to)114-124
Number of pages11
JournalJournal of Organometallic Chemistry
Volume633
Issue number1-2
DOIs
StatePublished - Aug 10 2001
Externally publishedYes

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Keywords

  • Acetylide
  • Electrochemistry
  • Gold
  • Hyperpolarizability
  • Ruthenium
  • Vinylidene
  • X-ray structure

ASJC Scopus subject areas

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

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