Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes

Stephanie K. Hurst, Marie P. Cifuentes, Andrew M. McDonagh, Mark G. Humphrey, Marek Samoc, Barry Luther-Davies, Inge Asselberghs, André Persoons

Research output: Contribution to journalArticle

88 Scopus citations

Abstract

The complexes [Au(4-CCC6H4NO2)(L)] [L=PCy3 (1), PMe3 (2)], [(L)Au(μ-4-CCRCC)Au(L)] [R=C6H4, L=PCy3 (4), PPh3 (5); R=C6H4-4-C6H4, L=PCy3 (7), PPh3 (8)], trans,trans-[RuCl(dppm)2(μ-4,4′-CCC6H4C6H4CC)RuCl(dppm)2] (11), trans-[Ru(X)(Y)(dppe)2] [X=Cl, Y=4-CCC6H4I (12), 4-CCC6H4CCSiMe3 (13); X=CCPh, 4-CCC6H4CCH (14)] and {trans-[Ru(CCPh)(dppe)2]}2(μ-4,4′-CCC6H4CCCCC6H4CC) (15) have been prepared and their electrochemical (Ru complexes) and nonlinear optical properties assessed. Electronic communication between the metal centers in 10, 11 and 15 diminishes as the π-delocalizable bridge is lengthened. Quadratic nonlinear optical (NLO) merit increases on replacing triarylphosphine by trialkylphosphine, the relative β values Au(4-CCC6H4NO2)(PPh3)<1<3 being observed. Cubic NLO values are small for the gold complexes and much larger for the ruthenium examples. Complex 15 has the largest σ2/MWt (two-photon absorption cross-section/molecular weight) value observed thus far for an organometallic complex.

Original languageEnglish (US)
Pages (from-to)259-267
Number of pages9
JournalJournal of Organometallic Chemistry
Volume642
Issue number1-2
DOIs
StatePublished - Jan 1 2002
Externally publishedYes

Keywords

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

ASJC Scopus subject areas

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

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