Synthesis and nonlinear optical properties of η5-monocyclopentadienyliron(II) acetylide derivatives. X-ray crystal structures

M. Helena Garcia, M. Paula Robalo, Alberto R. Dias, M. Teresa Duarte, Wim Wenseleers, G. Aerts, Etienne Goovaerts, Marie P. Cifuentes, Stephanie K Hurst, Mark G. Humphrey, Marek Samoc, Barry Luther-Davies

Research output: Contribution to journalArticle

62 Citations (Scopus)

Abstract

A series of new acetylide complexes of the type [Fe(η5-C5H5)(P down curve sign P)(p-C≡CC6H4R)] (P down curve sign P = DPPE (=l,2-bis(diphenylphosphino)ethane), (P)-PROPHOS (=R)-(+)-l,2-bis(diphenylphosphino)propane), R = NO2, C6H4NO2, (Z)-C(H)=C(H)C6H4NO2, (E)-C(H)=C(H)C6H4NO2) have been synthesized by halide abstraction from the precursors [Fe(η5-C5H5)(P down curve sign P)(I)] and fully characterized. Quadratic hyperpolarizabilities (β) for the complexes have been determined by hyper-Rayleigh scattering at 1064 nm. The influence on the nonlinear response of acetylide chain length in proceeding from 4-nitrophenylethynyl to 4-nitrobiphenylethynyl and 4-nitro-(E)-stibenylethynyl has been studied, revealing values of the first hyperpolarizabilities among the highest reported for organometallic molecular materials. Comparisons on the nonlinear efficiencies are drawn with the related well-known families of compounds [Ru(η5-C5H5)-(PR3)2(p -C≡C-(aryl)-NO2)] and [Fe(η5-C5H5)(P down curve sign P)(p-N≡C-(aryl)-NO2)]+. Cubic hyperpolarizabilities (γ) determined by Z-scan at 800 nm are consistent with an increase in γupon replacing Ru by the more easily oxidizable Fe and upon chain-lengthening the delocalizable π-bridging unit (proceeding from 4-C6H4 to (E)-4,4′-C6H4CH=CHC6H4). X-ray crystallographic structures of complexes [Fe(η5-C5H5(DPPE)(p-C≡CC6H 4NO2)] and [Fe(η5C5H5)(DPPE)((E)-p-C≡CC6 H4C(H)=C(H)C6H4NO2)] were studied in order to investigate the existence of π-back-donation suggested by spectroscopic and electrochemical data. Crystal packing was analyzed with the aim of assessing the alignment of the molecules in the lattice and hence suggesting the magnitude of NLO properties at the macroscopic level.

Original languageEnglish (US)
Pages (from-to)2107-2118
Number of pages12
JournalOrganometallics
Volume21
Issue number10
DOIs
StatePublished - May 13 2002
Externally publishedYes

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Optical properties
Crystal structure
Derivatives
optical properties
X rays
crystal structure
curves
synthesis
Propane
Rayleigh scattering
x rays
Organometallics
Chain length
propane
ethane
halides
Crystals
Molecules
alignment
1,2-dipalmitoyl-3-phosphatidylethanolamine

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Garcia, M. H., Robalo, M. P., Dias, A. R., Duarte, M. T., Wenseleers, W., Aerts, G., ... Luther-Davies, B. (2002). Synthesis and nonlinear optical properties of η5-monocyclopentadienyliron(II) acetylide derivatives. X-ray crystal structures. Organometallics, 21(10), 2107-2118. https://doi.org/10.1021/om0104619

Synthesis and nonlinear optical properties of η5-monocyclopentadienyliron(II) acetylide derivatives. X-ray crystal structures. / Garcia, M. Helena; Robalo, M. Paula; Dias, Alberto R.; Duarte, M. Teresa; Wenseleers, Wim; Aerts, G.; Goovaerts, Etienne; Cifuentes, Marie P.; Hurst, Stephanie K; Humphrey, Mark G.; Samoc, Marek; Luther-Davies, Barry.

In: Organometallics, Vol. 21, No. 10, 13.05.2002, p. 2107-2118.

Research output: Contribution to journalArticle

Garcia, MH, Robalo, MP, Dias, AR, Duarte, MT, Wenseleers, W, Aerts, G, Goovaerts, E, Cifuentes, MP, Hurst, SK, Humphrey, MG, Samoc, M & Luther-Davies, B 2002, 'Synthesis and nonlinear optical properties of η5-monocyclopentadienyliron(II) acetylide derivatives. X-ray crystal structures', Organometallics, vol. 21, no. 10, pp. 2107-2118. https://doi.org/10.1021/om0104619
Garcia, M. Helena ; Robalo, M. Paula ; Dias, Alberto R. ; Duarte, M. Teresa ; Wenseleers, Wim ; Aerts, G. ; Goovaerts, Etienne ; Cifuentes, Marie P. ; Hurst, Stephanie K ; Humphrey, Mark G. ; Samoc, Marek ; Luther-Davies, Barry. / Synthesis and nonlinear optical properties of η5-monocyclopentadienyliron(II) acetylide derivatives. X-ray crystal structures. In: Organometallics. 2002 ; Vol. 21, No. 10. pp. 2107-2118.
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T1 - Synthesis and nonlinear optical properties of η5-monocyclopentadienyliron(II) acetylide derivatives. X-ray crystal structures

AU - Garcia, M. Helena

AU - Robalo, M. Paula

AU - Dias, Alberto R.

AU - Duarte, M. Teresa

AU - Wenseleers, Wim

AU - Aerts, G.

AU - Goovaerts, Etienne

AU - Cifuentes, Marie P.

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AU - Humphrey, Mark G.

AU - Samoc, Marek

AU - Luther-Davies, Barry

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N2 - A series of new acetylide complexes of the type [Fe(η5-C5H5)(P down curve sign P)(p-C≡CC6H4R)] (P down curve sign P = DPPE (=l,2-bis(diphenylphosphino)ethane), (P)-PROPHOS (=R)-(+)-l,2-bis(diphenylphosphino)propane), R = NO2, C6H4NO2, (Z)-C(H)=C(H)C6H4NO2, (E)-C(H)=C(H)C6H4NO2) have been synthesized by halide abstraction from the precursors [Fe(η5-C5H5)(P down curve sign P)(I)] and fully characterized. Quadratic hyperpolarizabilities (β) for the complexes have been determined by hyper-Rayleigh scattering at 1064 nm. The influence on the nonlinear response of acetylide chain length in proceeding from 4-nitrophenylethynyl to 4-nitrobiphenylethynyl and 4-nitro-(E)-stibenylethynyl has been studied, revealing values of the first hyperpolarizabilities among the highest reported for organometallic molecular materials. Comparisons on the nonlinear efficiencies are drawn with the related well-known families of compounds [Ru(η5-C5H5)-(PR3)2(p -C≡C-(aryl)-NO2)] and [Fe(η5-C5H5)(P down curve sign P)(p-N≡C-(aryl)-NO2)]+. Cubic hyperpolarizabilities (γ) determined by Z-scan at 800 nm are consistent with an increase in γupon replacing Ru by the more easily oxidizable Fe and upon chain-lengthening the delocalizable π-bridging unit (proceeding from 4-C6H4 to (E)-4,4′-C6H4CH=CHC6H4). X-ray crystallographic structures of complexes [Fe(η5-C5H5(DPPE)(p-C≡CC6H 4NO2)] and [Fe(η5C5H5)(DPPE)((E)-p-C≡CC6 H4C(H)=C(H)C6H4NO2)] were studied in order to investigate the existence of π-back-donation suggested by spectroscopic and electrochemical data. Crystal packing was analyzed with the aim of assessing the alignment of the molecules in the lattice and hence suggesting the magnitude of NLO properties at the macroscopic level.

AB - A series of new acetylide complexes of the type [Fe(η5-C5H5)(P down curve sign P)(p-C≡CC6H4R)] (P down curve sign P = DPPE (=l,2-bis(diphenylphosphino)ethane), (P)-PROPHOS (=R)-(+)-l,2-bis(diphenylphosphino)propane), R = NO2, C6H4NO2, (Z)-C(H)=C(H)C6H4NO2, (E)-C(H)=C(H)C6H4NO2) have been synthesized by halide abstraction from the precursors [Fe(η5-C5H5)(P down curve sign P)(I)] and fully characterized. Quadratic hyperpolarizabilities (β) for the complexes have been determined by hyper-Rayleigh scattering at 1064 nm. The influence on the nonlinear response of acetylide chain length in proceeding from 4-nitrophenylethynyl to 4-nitrobiphenylethynyl and 4-nitro-(E)-stibenylethynyl has been studied, revealing values of the first hyperpolarizabilities among the highest reported for organometallic molecular materials. Comparisons on the nonlinear efficiencies are drawn with the related well-known families of compounds [Ru(η5-C5H5)-(PR3)2(p -C≡C-(aryl)-NO2)] and [Fe(η5-C5H5)(P down curve sign P)(p-N≡C-(aryl)-NO2)]+. Cubic hyperpolarizabilities (γ) determined by Z-scan at 800 nm are consistent with an increase in γupon replacing Ru by the more easily oxidizable Fe and upon chain-lengthening the delocalizable π-bridging unit (proceeding from 4-C6H4 to (E)-4,4′-C6H4CH=CHC6H4). X-ray crystallographic structures of complexes [Fe(η5-C5H5(DPPE)(p-C≡CC6H 4NO2)] and [Fe(η5C5H5)(DPPE)((E)-p-C≡CC6 H4C(H)=C(H)C6H4NO2)] were studied in order to investigate the existence of π-back-donation suggested by spectroscopic and electrochemical data. Crystal packing was analyzed with the aim of assessing the alignment of the molecules in the lattice and hence suggesting the magnitude of NLO properties at the macroscopic level.

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