Organometallic complexes for nonlinear optics. Part 29. Quadratic and cubic hyperpolarizabilities of stilbenylethynyl-gold and -ruthenium complexes

Stephanie K Hurst, Nigel T. Lucas, Mark G. Humphrey, Takashi Isoshima, Kurt Wostyn, Inge Asselberghs, Koen Clays, André Persoons, Marek Samoc, Barry Luther-Davies

Research output: Contribution to journalArticle

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Abstract

The compounds (E)-4-XC≡CC6H4CH=CHPh [X=SiMe3 (1), H (2)], 1,3,5-{(E)-4-XC6H 4CH=CH}3C6H3 [X=I (3), C≡CSiMe3 (4), C≡CH (5)], [Au{(E)-4-C≡CC 6H4CH=CHPh}(L)] [L=PPh3 (6), PMe3 (7)], [Au(4-C≡CC6H4C≡CPh)(L)] [L=PPh 3 (8), PMe3 (9)], 1,3,5-[(Ph3P)Au{(E)-4- C≡CC6H4CH=CH}]3C6H 3 (10), trans-[Ru{(E)-4-C=CHC6H4CH=CHPh} Cl(dppm)2]PF6 (11), trans-[Ru{(E)-4-C≡CC 6H4CH=CHPh}Cl(L2)2] [L 2=dppm (12), dppe (13)], [1,3,5-(trans-[(dppm)2ClRu{(E)-4- C=CHC6H4CH=CH}])3C6H 3](PF6)3 (14), 1,3,5-(trans-[(L 2)2ClRu{(E)-4-C≡CC6H4CH=CH}]) 3C6H3 [L2=dppm (15), dppe (16)] and 1,3,5-(trans-[(dppe)2(PhC≡C)Ru{(E)-4-C≡CC 6H4CH=CH}])3C6H3 (17) have been prepared (and the identity of 6 confirmed by a single-crystal X-ray diffraction study), and their electrochemical (Ru complexes) and nonlinear optical (NLO) properties assessed. The ruthenium complexes display reversible (12, 13, 15-17) or nonreversible (11, 14) processes attributable to Ru-centered oxidation, at potentials similar to those of previously-investigated monoruthenium alkynyl or vinylidene complexes. No evidence for intermetallic electronic communication in 14-17 is observed. Quadratic nonlinearities at 1064 and 800 nm for the octopolar stilbenyl-ruthenium complexes 14, 15 are large for compounds without strongly accepting substituents. Cubic molecular hyperpolarizabilities at 800 nm for the organic compounds and gold complexes are low. Cubic nonlinearities |γ|800 and two-photon absorption (TPA) cross-sections σ2 for the ruthenium complexes increase on proceeding from linear analogues 12, 13 to octopolar complexes 15, 16; the latter and 17 possess some of the largest |γ|800 and σ2 values for organometallics thus far. Cubic nonlinearities Im(χ(3))/N for 13, 16, and 17 from the first application of electroabsorption (EA) spectroscopy to organometallics are also large, scaling with the number of metal atoms.

Original languageEnglish (US)
Pages (from-to)62-76
Number of pages15
JournalInorganica Chimica Acta
Volume350
DOIs
StatePublished - Jul 4 2003
Externally publishedYes

Fingerprint

Nonlinear optics
Ruthenium
nonlinear optics
Organometallics
Gold
ruthenium
methylidyne
gold
Gold Compounds
nonlinearity
Photons
Organic compounds
X-Ray Diffraction
Intermetallics
Spectrum Analysis
Optical properties
Metals
Single crystals
Spectroscopy
X ray diffraction

Keywords

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

ASJC Scopus subject areas

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

Cite this

Organometallic complexes for nonlinear optics. Part 29. Quadratic and cubic hyperpolarizabilities of stilbenylethynyl-gold and -ruthenium complexes. / Hurst, Stephanie K; Lucas, Nigel T.; Humphrey, Mark G.; Isoshima, Takashi; Wostyn, Kurt; Asselberghs, Inge; Clays, Koen; Persoons, André; Samoc, Marek; Luther-Davies, Barry.

In: Inorganica Chimica Acta, Vol. 350, 04.07.2003, p. 62-76.

Research output: Contribution to journalArticle

Hurst, SK, Lucas, NT, Humphrey, MG, Isoshima, T, Wostyn, K, Asselberghs, I, Clays, K, Persoons, A, Samoc, M & Luther-Davies, B 2003, 'Organometallic complexes for nonlinear optics. Part 29. Quadratic and cubic hyperpolarizabilities of stilbenylethynyl-gold and -ruthenium complexes', Inorganica Chimica Acta, vol. 350, pp. 62-76. https://doi.org/10.1016/S0020-1693(02)01497-4
Hurst, Stephanie K ; Lucas, Nigel T. ; Humphrey, Mark G. ; Isoshima, Takashi ; Wostyn, Kurt ; Asselberghs, Inge ; Clays, Koen ; Persoons, André ; Samoc, Marek ; Luther-Davies, Barry. / Organometallic complexes for nonlinear optics. Part 29. Quadratic and cubic hyperpolarizabilities of stilbenylethynyl-gold and -ruthenium complexes. In: Inorganica Chimica Acta. 2003 ; Vol. 350. pp. 62-76.
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abstract = "The compounds (E)-4-XC≡CC6H4CH=CHPh [X=SiMe3 (1), H (2)], 1,3,5-{(E)-4-XC6H 4CH=CH}3C6H3 [X=I (3), C≡CSiMe3 (4), C≡CH (5)], [Au{(E)-4-C≡CC 6H4CH=CHPh}(L)] [L=PPh3 (6), PMe3 (7)], [Au(4-C≡CC6H4C≡CPh)(L)] [L=PPh 3 (8), PMe3 (9)], 1,3,5-[(Ph3P)Au{(E)-4- C≡CC6H4CH=CH}]3C6H 3 (10), trans-[Ru{(E)-4-C=CHC6H4CH=CHPh} Cl(dppm)2]PF6 (11), trans-[Ru{(E)-4-C≡CC 6H4CH=CHPh}Cl(L2)2] [L 2=dppm (12), dppe (13)], [1,3,5-(trans-[(dppm)2ClRu{(E)-4- C=CHC6H4CH=CH}])3C6H 3](PF6)3 (14), 1,3,5-(trans-[(L 2)2ClRu{(E)-4-C≡CC6H4CH=CH}]) 3C6H3 [L2=dppm (15), dppe (16)] and 1,3,5-(trans-[(dppe)2(PhC≡C)Ru{(E)-4-C≡CC 6H4CH=CH}])3C6H3 (17) have been prepared (and the identity of 6 confirmed by a single-crystal X-ray diffraction study), and their electrochemical (Ru complexes) and nonlinear optical (NLO) properties assessed. The ruthenium complexes display reversible (12, 13, 15-17) or nonreversible (11, 14) processes attributable to Ru-centered oxidation, at potentials similar to those of previously-investigated monoruthenium alkynyl or vinylidene complexes. No evidence for intermetallic electronic communication in 14-17 is observed. Quadratic nonlinearities at 1064 and 800 nm for the octopolar stilbenyl-ruthenium complexes 14, 15 are large for compounds without strongly accepting substituents. Cubic molecular hyperpolarizabilities at 800 nm for the organic compounds and gold complexes are low. Cubic nonlinearities |γ|800 and two-photon absorption (TPA) cross-sections σ2 for the ruthenium complexes increase on proceeding from linear analogues 12, 13 to octopolar complexes 15, 16; the latter and 17 possess some of the largest |γ|800 and σ2 values for organometallics thus far. Cubic nonlinearities Im(χ(3))/N for 13, 16, and 17 from the first application of electroabsorption (EA) spectroscopy to organometallics are also large, scaling with the number of metal atoms.",
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TY - JOUR

T1 - Organometallic complexes for nonlinear optics. Part 29. Quadratic and cubic hyperpolarizabilities of stilbenylethynyl-gold and -ruthenium complexes

AU - Hurst, Stephanie K

AU - Lucas, Nigel T.

AU - Humphrey, Mark G.

AU - Isoshima, Takashi

AU - Wostyn, Kurt

AU - Asselberghs, Inge

AU - Clays, Koen

AU - Persoons, André

AU - Samoc, Marek

AU - Luther-Davies, Barry

PY - 2003/7/4

Y1 - 2003/7/4

N2 - The compounds (E)-4-XC≡CC6H4CH=CHPh [X=SiMe3 (1), H (2)], 1,3,5-{(E)-4-XC6H 4CH=CH}3C6H3 [X=I (3), C≡CSiMe3 (4), C≡CH (5)], [Au{(E)-4-C≡CC 6H4CH=CHPh}(L)] [L=PPh3 (6), PMe3 (7)], [Au(4-C≡CC6H4C≡CPh)(L)] [L=PPh 3 (8), PMe3 (9)], 1,3,5-[(Ph3P)Au{(E)-4- C≡CC6H4CH=CH}]3C6H 3 (10), trans-[Ru{(E)-4-C=CHC6H4CH=CHPh} Cl(dppm)2]PF6 (11), trans-[Ru{(E)-4-C≡CC 6H4CH=CHPh}Cl(L2)2] [L 2=dppm (12), dppe (13)], [1,3,5-(trans-[(dppm)2ClRu{(E)-4- C=CHC6H4CH=CH}])3C6H 3](PF6)3 (14), 1,3,5-(trans-[(L 2)2ClRu{(E)-4-C≡CC6H4CH=CH}]) 3C6H3 [L2=dppm (15), dppe (16)] and 1,3,5-(trans-[(dppe)2(PhC≡C)Ru{(E)-4-C≡CC 6H4CH=CH}])3C6H3 (17) have been prepared (and the identity of 6 confirmed by a single-crystal X-ray diffraction study), and their electrochemical (Ru complexes) and nonlinear optical (NLO) properties assessed. The ruthenium complexes display reversible (12, 13, 15-17) or nonreversible (11, 14) processes attributable to Ru-centered oxidation, at potentials similar to those of previously-investigated monoruthenium alkynyl or vinylidene complexes. No evidence for intermetallic electronic communication in 14-17 is observed. Quadratic nonlinearities at 1064 and 800 nm for the octopolar stilbenyl-ruthenium complexes 14, 15 are large for compounds without strongly accepting substituents. Cubic molecular hyperpolarizabilities at 800 nm for the organic compounds and gold complexes are low. Cubic nonlinearities |γ|800 and two-photon absorption (TPA) cross-sections σ2 for the ruthenium complexes increase on proceeding from linear analogues 12, 13 to octopolar complexes 15, 16; the latter and 17 possess some of the largest |γ|800 and σ2 values for organometallics thus far. Cubic nonlinearities Im(χ(3))/N for 13, 16, and 17 from the first application of electroabsorption (EA) spectroscopy to organometallics are also large, scaling with the number of metal atoms.

AB - The compounds (E)-4-XC≡CC6H4CH=CHPh [X=SiMe3 (1), H (2)], 1,3,5-{(E)-4-XC6H 4CH=CH}3C6H3 [X=I (3), C≡CSiMe3 (4), C≡CH (5)], [Au{(E)-4-C≡CC 6H4CH=CHPh}(L)] [L=PPh3 (6), PMe3 (7)], [Au(4-C≡CC6H4C≡CPh)(L)] [L=PPh 3 (8), PMe3 (9)], 1,3,5-[(Ph3P)Au{(E)-4- C≡CC6H4CH=CH}]3C6H 3 (10), trans-[Ru{(E)-4-C=CHC6H4CH=CHPh} Cl(dppm)2]PF6 (11), trans-[Ru{(E)-4-C≡CC 6H4CH=CHPh}Cl(L2)2] [L 2=dppm (12), dppe (13)], [1,3,5-(trans-[(dppm)2ClRu{(E)-4- C=CHC6H4CH=CH}])3C6H 3](PF6)3 (14), 1,3,5-(trans-[(L 2)2ClRu{(E)-4-C≡CC6H4CH=CH}]) 3C6H3 [L2=dppm (15), dppe (16)] and 1,3,5-(trans-[(dppe)2(PhC≡C)Ru{(E)-4-C≡CC 6H4CH=CH}])3C6H3 (17) have been prepared (and the identity of 6 confirmed by a single-crystal X-ray diffraction study), and their electrochemical (Ru complexes) and nonlinear optical (NLO) properties assessed. The ruthenium complexes display reversible (12, 13, 15-17) or nonreversible (11, 14) processes attributable to Ru-centered oxidation, at potentials similar to those of previously-investigated monoruthenium alkynyl or vinylidene complexes. No evidence for intermetallic electronic communication in 14-17 is observed. Quadratic nonlinearities at 1064 and 800 nm for the octopolar stilbenyl-ruthenium complexes 14, 15 are large for compounds without strongly accepting substituents. Cubic molecular hyperpolarizabilities at 800 nm for the organic compounds and gold complexes are low. Cubic nonlinearities |γ|800 and two-photon absorption (TPA) cross-sections σ2 for the ruthenium complexes increase on proceeding from linear analogues 12, 13 to octopolar complexes 15, 16; the latter and 17 possess some of the largest |γ|800 and σ2 values for organometallics thus far. Cubic nonlinearities Im(χ(3))/N for 13, 16, and 17 from the first application of electroabsorption (EA) spectroscopy to organometallics are also large, scaling with the number of metal atoms.

KW - Acetylide

KW - Electrochemistry

KW - Gold

KW - Hyperpolarizability

KW - Nonlinear optics

KW - Ruthenium

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