Title: Organometallic complexes for nonlinear optics - Part 23. Quadratic and cubic hyperpolarizabilities of acetylide and vinylidene complexes derived from protected and free formylphenylacetylenes
Authors: Hurst, SK ×
Lucas, NT
Cifuentes, MP
Humphrey, MG
Samoc, M
Luther-Davies, B
Asselberghs, Inge
Van Boxel, Roel
Persoons, Andre #
Issue Date: Jan-2001
Publisher: Elsevier science sa
Series Title: Journal of Organometallic Chemistry vol:633 issue:1-2 pages:114-124
Abstract: The acetylenes 4-HC drop CC6H4R [R=CH{OC(O)Me}(2) (1), CHO(CH2)(3)O (2)], ruthenium complexes [Ru(4-C drop CC6H4R)(PPh3)(2)- (eta -C5H5)] [R = CH{OC(O)Me}(2) (3), CHO (4)], [Ru(n-C=CHC6H4R)Cl(dppm)(2)]PF6 [n = 4, R = CHO(CH2)(3)O (7); R = CHO, n = 3 (11), 2 (15)], and [Ru(n-C drop CC6H4R)Cl(dppm)(2)] [n = 4, R = CHO(CH2)(3)O (8); n = 3, R = CHO (12)], and gold complexes [Au(n-C drop CC6H4R)(L)] [n = 4, R = CHO, L = PPh3 (5), PMe3 (6); n = 4, R = CHO(CH2)(3)O, L = PPh3 (9), PMe3 (10); n = 3 R = CHO, L = PPh3 (13), PMe3 (14)] have been prepared, and 9 characterized by a single crystal X-ray diffraction study. Electrochemical data for the ruthenium complexes reveal reversible or quasi-reversible (alkynyl complexes) or irreversible (vinylidene complexes) processes assigned to the Ru-II/III couple; the effect on E-1/2 values of the various structural modifications across 3, 4, 7, 8, 11, 12 and 15 are discussed. The molecular quadratic and cubic optical nonlinearities of 1-15 have been determined by the hyper-Rayleigh scattering technique at 1064 mn and the Z-scan technique at 800 nm. respectively; beta values increase on increasing the acceptor strength, proceeding from 3-acceptor-substituted to 4-acceptor-substituted arylalkynyl ligand, and an increasing phosphine donor strength, whereas gamma values increase on increasing the number of phosphine aryl groups (i.e. increasing delocalization) proceeding from PMe3 to PPh3-containing complex. (C) 2001 Published by Elsevier Science B.V.
ISSN: 0022-328X
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
Chemistry - miscellaneous
× corresponding author
# (joint) last author

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