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

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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
StatePublished - 2002
Externally publishedYes

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Nonlinear optics
Ruthenium
nonlinear optics
Organometallics
Gold
absorption cross sections
ruthenium
molecular weight
Photons
Optical properties
communication
Molecular weight
gold
optical properties
Communication
photons
Metals
electronics
metals
Molecular Weight

Keywords

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

ASJC Scopus subject areas

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

Cite this

Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes. / Hurst, Stephanie K; Cifuentes, Marie P.; McDonagh, Andrew M.; Humphrey, Mark G.; Samoc, Marek; Luther-Davies, Barry; Asselberghs, Inge; Persoons, André.

In: Journal of Organometallic Chemistry, Vol. 642, No. 1-2, 2002, p. 259-267.

Research output: Contribution to journalArticle

Hurst, SK, Cifuentes, MP, McDonagh, AM, Humphrey, MG, Samoc, M, Luther-Davies, B, Asselberghs, I & Persoons, A 2002, 'Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes', Journal of Organometallic Chemistry, vol. 642, no. 1-2, pp. 259-267.
Hurst, Stephanie K ; Cifuentes, Marie P. ; McDonagh, Andrew M. ; Humphrey, Mark G. ; Samoc, Marek ; Luther-Davies, Barry ; Asselberghs, Inge ; Persoons, André. / Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes. In: Journal of Organometallic Chemistry. 2002 ; Vol. 642, No. 1-2. pp. 259-267.
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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.",
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T1 - Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes

AU - Hurst, Stephanie K

AU - Cifuentes, Marie P.

AU - McDonagh, Andrew M.

AU - Humphrey, Mark G.

AU - Samoc, Marek

AU - Luther-Davies, Barry

AU - Asselberghs, Inge

AU - Persoons, André

PY - 2002

Y1 - 2002

N2 - 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.

AB - 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.

KW - Acetylide

KW - Electrochemistry

KW - Gold

KW - Hyperpolarizability

KW - Nonlinear optics

KW - Ruthenium

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M3 - Article

VL - 642

SP - 259

EP - 267

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1-2

ER -