Organometallic complexes for nonlinear optics. Part 27. Syntheses and optical properties of some iron, ruthenium and osmium alkynyl complexes

Clem E. Powell, Marie P. Cifuentes, Andrew M. McDonagh, Stephanie K. Hurst, Nigel T. Lucas, Christopher D. Delfs, Robert Stranger, Mark G. Humphrey, Stephan Houbrechts, Inge Asselberghs, André Persoons, David C R Hockless

Research output: Contribution to journalArticle

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Abstract

The syntheses of the alkynyl complexes M(4-C≡CC6H4NO2)(dppe)(η-C 5H5) [M=Fe (1), Ru (2), Os (3)], Os(4-C≡CC6H4NO2)(PPh3) 2(η-C5H5) (4) and Ru(4-C≡CC6H4NO2)(CO)2 (η-C5H5) (5) are reported. Structural studies reveal a decrease in Ru-C(1) distance on proceeding from 5 to 2, consistent with greater back-donation of electron density to the alkynyl ligand from the more electron-rich metal center in 2. Electrochemical data show that the MII/III couple for the dicarbonyl complex 5 is at a significantly more positive potential than that of the related diphosphine complex 2, consistent with ligand variation modifying the electron richness and hence donor strength of the metal center. Time-dependent density functional calculations on model complexes M(4-C≡CC6H4NO2)(PH3) 2(η-C5H5) (M=Fe, Ru, Os) have been employed to assign the intense low-energy optical transition in these complexes as MLCT in character, the higher energy band being phenyl-phenyl* in nature. Molecular quadratic optical nonlinearities have been measured using the hyper-Rayleigh scattering procedure at 1064 nm. β values vary as Fe≤Ru≤Os for metal variation and CO<phosphines for co-ligand variation, the latter consistent with the variation in donor strength of the metal center inferred from electrochemical and crystallographic data. The observed trend in β on metal variation follows the trend in backbonding energies calculated by DFT.

Original languageEnglish (US)
Pages (from-to)9-18
Number of pages10
JournalInorganica Chimica Acta
Volume352
DOIs
StatePublished - Aug 6 2003
Externally publishedYes

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Osmium
Nonlinear optics
Ruthenium
osmium
nonlinear optics
Organometallics
ruthenium
Iron
Optical properties
Metals
optical properties
iron
synthesis
metals
Ligands
Electrons
ligands
Phosphines
trends
Rayleigh scattering

Keywords

  • Alkynyl
  • Cyclic voltammetry
  • Density functional theory
  • Iron
  • NLO
  • Osmium
  • Ruthenium
  • X-ray structure

ASJC Scopus subject areas

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

Cite this

Organometallic complexes for nonlinear optics. Part 27. Syntheses and optical properties of some iron, ruthenium and osmium alkynyl complexes. / Powell, Clem E.; Cifuentes, Marie P.; McDonagh, Andrew M.; Hurst, Stephanie K.; Lucas, Nigel T.; Delfs, Christopher D.; Stranger, Robert; Humphrey, Mark G.; Houbrechts, Stephan; Asselberghs, Inge; Persoons, André; Hockless, David C R.

In: Inorganica Chimica Acta, Vol. 352, 06.08.2003, p. 9-18.

Research output: Contribution to journalArticle

Powell, CE, Cifuentes, MP, McDonagh, AM, Hurst, SK, Lucas, NT, Delfs, CD, Stranger, R, Humphrey, MG, Houbrechts, S, Asselberghs, I, Persoons, A & Hockless, DCR 2003, 'Organometallic complexes for nonlinear optics. Part 27. Syntheses and optical properties of some iron, ruthenium and osmium alkynyl complexes', Inorganica Chimica Acta, vol. 352, pp. 9-18. https://doi.org/10.1016/S0020-1693(03)00126-9
Powell, Clem E. ; Cifuentes, Marie P. ; McDonagh, Andrew M. ; Hurst, Stephanie K. ; Lucas, Nigel T. ; Delfs, Christopher D. ; Stranger, Robert ; Humphrey, Mark G. ; Houbrechts, Stephan ; Asselberghs, Inge ; Persoons, André ; Hockless, David C R. / Organometallic complexes for nonlinear optics. Part 27. Syntheses and optical properties of some iron, ruthenium and osmium alkynyl complexes. In: Inorganica Chimica Acta. 2003 ; Vol. 352. pp. 9-18.
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abstract = "The syntheses of the alkynyl complexes M(4-C≡CC6H4NO2)(dppe)(η-C 5H5) [M=Fe (1), Ru (2), Os (3)], Os(4-C≡CC6H4NO2)(PPh3) 2(η-C5H5) (4) and Ru(4-C≡CC6H4NO2)(CO)2 (η-C5H5) (5) are reported. Structural studies reveal a decrease in Ru-C(1) distance on proceeding from 5 to 2, consistent with greater back-donation of electron density to the alkynyl ligand from the more electron-rich metal center in 2. Electrochemical data show that the MII/III couple for the dicarbonyl complex 5 is at a significantly more positive potential than that of the related diphosphine complex 2, consistent with ligand variation modifying the electron richness and hence donor strength of the metal center. Time-dependent density functional calculations on model complexes M(4-C≡CC6H4NO2)(PH3) 2(η-C5H5) (M=Fe, Ru, Os) have been employed to assign the intense low-energy optical transition in these complexes as MLCT in character, the higher energy band being phenyl-phenyl* in nature. Molecular quadratic optical nonlinearities have been measured using the hyper-Rayleigh scattering procedure at 1064 nm. β values vary as Fe≤Ru≤Os for metal variation and CO",
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AU - Powell, Clem E.

AU - Cifuentes, Marie P.

AU - McDonagh, Andrew M.

AU - Hurst, Stephanie K.

AU - Lucas, Nigel T.

AU - Delfs, Christopher D.

AU - Stranger, Robert

AU - Humphrey, Mark G.

AU - Houbrechts, Stephan

AU - Asselberghs, Inge

AU - Persoons, André

AU - Hockless, David C R

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N2 - The syntheses of the alkynyl complexes M(4-C≡CC6H4NO2)(dppe)(η-C 5H5) [M=Fe (1), Ru (2), Os (3)], Os(4-C≡CC6H4NO2)(PPh3) 2(η-C5H5) (4) and Ru(4-C≡CC6H4NO2)(CO)2 (η-C5H5) (5) are reported. Structural studies reveal a decrease in Ru-C(1) distance on proceeding from 5 to 2, consistent with greater back-donation of electron density to the alkynyl ligand from the more electron-rich metal center in 2. Electrochemical data show that the MII/III couple for the dicarbonyl complex 5 is at a significantly more positive potential than that of the related diphosphine complex 2, consistent with ligand variation modifying the electron richness and hence donor strength of the metal center. Time-dependent density functional calculations on model complexes M(4-C≡CC6H4NO2)(PH3) 2(η-C5H5) (M=Fe, Ru, Os) have been employed to assign the intense low-energy optical transition in these complexes as MLCT in character, the higher energy band being phenyl-phenyl* in nature. Molecular quadratic optical nonlinearities have been measured using the hyper-Rayleigh scattering procedure at 1064 nm. β values vary as Fe≤Ru≤Os for metal variation and CO

AB - The syntheses of the alkynyl complexes M(4-C≡CC6H4NO2)(dppe)(η-C 5H5) [M=Fe (1), Ru (2), Os (3)], Os(4-C≡CC6H4NO2)(PPh3) 2(η-C5H5) (4) and Ru(4-C≡CC6H4NO2)(CO)2 (η-C5H5) (5) are reported. Structural studies reveal a decrease in Ru-C(1) distance on proceeding from 5 to 2, consistent with greater back-donation of electron density to the alkynyl ligand from the more electron-rich metal center in 2. Electrochemical data show that the MII/III couple for the dicarbonyl complex 5 is at a significantly more positive potential than that of the related diphosphine complex 2, consistent with ligand variation modifying the electron richness and hence donor strength of the metal center. Time-dependent density functional calculations on model complexes M(4-C≡CC6H4NO2)(PH3) 2(η-C5H5) (M=Fe, Ru, Os) have been employed to assign the intense low-energy optical transition in these complexes as MLCT in character, the higher energy band being phenyl-phenyl* in nature. Molecular quadratic optical nonlinearities have been measured using the hyper-Rayleigh scattering procedure at 1064 nm. β values vary as Fe≤Ru≤Os for metal variation and CO

KW - Alkynyl

KW - Cyclic voltammetry

KW - Density functional theory

KW - Iron

KW - NLO

KW - Osmium

KW - Ruthenium

KW - X-ray structure

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JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

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