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

Powell, CE; Cifuentes, MP; McDonagh, AM; Hurst, SK; Lucas, NT; Delfs, CD; Stranger, R; Humphrey, MG; Houbrechts, S; Asselberghs, I; Persoons, A; Hockless, DCR

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

Powell, CE Cifuentes, MP McDonagh, AM

Hurst, SK Lucas, NT Delfs, CD Stranger, R Humphrey, MG Houbrechts, S Asselberghs, I Persoons, A Hockless, DCR

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Publication Type:: Journal Article
Citation:: Inorganica Chimica Acta, 2003, 352 pp. 9 - 18
Issue Date:: 2003-08-06

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Field	Value	Language
dc.contributor.author	Powell, CE	en_US
dc.contributor.author	Cifuentes, MP	en_US
dc.contributor.author	McDonagh, AM https://orcid.org/0000-0002-9502-1175	en_US
dc.contributor.author	Hurst, SK	en_US
dc.contributor.author	Lucas, NT	en_US
dc.contributor.author	Delfs, CD	en_US
dc.contributor.author	Stranger, R	en_US
dc.contributor.author	Humphrey, MG	en_US
dc.contributor.author	Houbrechts, S	en_US
dc.contributor.author	Asselberghs, I	en_US
dc.contributor.author	Persoons, A	en_US
dc.contributor.author	Hockless, DCR	en_US
dc.date.issued	2003-08-06	en_US
dc.identifier.citation	Inorganica Chimica Acta, 2003, 352 pp. 9 - 18	en_US
dc.identifier.issn	0020-1693	en_US
dc.identifier.uri	http://hdl.handle.net/10453/514
dc.description.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. © 2003 Elsevier Science B.V. All rights reserved.	en_US
dc.relation.ispartof	Inorganica Chimica Acta	en_US
dc.relation.isbasedon	10.1016/S0020-1693(03)00126-9	en_US
dc.subject.classification	Inorganic & Nuclear Chemistry	en_US
dc.title	Organometallic complexes for nonlinear optics. Part 27. Syntheses and optical properties of some iron, ruthenium and osmium alkynyl complexes	en_US
dc.type	Journal Article
utslib.citation.volume	352	en_US
utslib.for	0302 Inorganic Chemistry	en_US
utslib.for	0306 Physical Chemistry (incl. Structural)	en_US
utslib.for	0399 Other Chemical Sciences	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
pubs.organisational-group	/University of Technology Sydney/Strength - CCET - Centre for Clean Energy Technology
utslib.copyright.status	closed_access
pubs.publication-status	Published	en_US
pubs.volume	352	en_US

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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