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Title: Organometallic complexes for nonlinear optics. X. Molecular quadratic and cubic hyperpolarizabilities of systematically varied (cyclopentadienyl) bis(phosphine)ruthenium sigma-arylacetylides: X-ray crystal structure of Ru((E)-4,4 '-C CC6H4CH=CHC6H4NO2)(PPh3)(2)(eta-C5H5)
Authors: Whittall, IR ×
Cifuentes, MP
Humphrey, MG
Luther-Davies, B
Samoc, M
Houbrechts, Stephan
Persoons, Andre
Heath, GA
Hockless, DCR #
Issue Date: Jan-1997
Publisher: Elsevier science sa
Series Title: Journal of Organometallic Chemistry vol:549 issue:1-2 pages:127-137
Abstract: The complexes Ru(4,4'-CC6H4C6H4NO2)PPh3)(2)(eta-C5H5) and Ru(4,4'-C drop CC6H4C drop CC6H4NO2)(PPh3),(eta-C5H5) have been prepared and the latter structurally characterized; they belong to a series of organometallic donor-bridge-acceptor compounds containing (cyclopentadienyl)bis(phosphine)ruthenium(II) centres as donors, conjugated arylacetylide bridges, and nitro acceptor groups. Electrochemical data for the series of complexes Ru(C drop CR)(PR'(3))(2)(eta-C5H5) (R=Ph, 4-C6H4NO2, R'=Ph, Me; R=4,4'-C6H4C6H4NO2, (E)-4,4'-C6H4CH=CHC6H4NO2, 4,4'-C6H4C drop CC6H4NO2, 4,4'-C6H4N=CHC6H4NO2, R'=Ph) are consistent with an Ru-II/III couple whose oxidation potentials vary strongly with chain-lengthening from one-ring to two-ring acetylide ligand, but show little variation with changes at the bridging unit of the two-ring acetylide ligand. The molecular quadratic and cubic optical nonlinearities of the series of complexes have been determined by hyper-Rayleigh scattering (HRS) and Z-scan techniques, respectively. Molecular first hyperpolarizabilities by HRS at 1064 nm are dispersively enhanced; experimental and two-level corrected data suggest an increase in nonlinearity on chain-lengthening of the bridge, in proceeding from C6H4 to C6H4C6H4 and then C6H4C drop CC6H4 and C6H4CH=CHC6H4, a general trend that is reproduced by semiempirical ZINDO computations. Cubic hyperpolarizabilities by Z-scan at 800 nm are negative for complexes with nitro acceptor groups, probably a result of two-photon dispersion, with absolute values (up to 850 X 10(-36) esu) large for small organometallic complexes; as with quadratic nonlinearities, cubic nonlinearities increase substantially on bridge lengthening, with little variation on phosphine substitution. (C) 1997 Elsevier Science S.A.
ISSN: 0022-328X
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

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