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Title: Organometallic complexes for nonlinear optics Part 19. Syntheses and molecular quadratic hyperpolarizabilities of indoanilino-alkynyl-ruthenium complexes
Authors: McDonagh, AM ×
Cifuentes, MP
Lucas, NT
Humphrey, MG
Houbrechts, Stephan
Persoons, Andre #
Issue Date: Jan-2000
Publisher: Elsevier science sa
Series Title: Journal of Organometallic Chemistry vol:605 issue:2 pages:184-192
Abstract: The terminal alkyne 4-HC=CC6H4N=CCH=C'BuC(O)C'Bu=CH (1) and ruthenium complex derivatives trans-[Ru(C=C-4-C6H4N=CCH = C'BuC(O)C'Bu=CH}Cl(dppm)(2)] (2) and [Ru{C=C-4-C6H4N=CCH=C'BuC(O)C'BuC(O)C'Bu=CH}(PPh3)(2)(eta-C5H5)] (3) have been synthesized. An X-ray structural study of 3 reveals the expected equivalent C-C bond lengths of the phenyl and alternating C-C and C=C bond lengths of the quinonal ring in the indoanilino-alkynyl ligand; there is a dihedral angle of 47.59 degrees between the phenyl and quinonal rings, probably a result of ortho-hydrogen repulsion. Metal-centred oxidation potentials of 2 and 3 are similar to those of 'extended chain' 4-nitroaryl-alkynyl complex analogues. Irreversible quinonal ring-centred reductions occur at significantly more negative potentials than the quasi-reversible reductions in their nitro-containing analogues. Quadratic optical nonlinearities by hyper-Rayleigh scattering at 1064 nm for 2 (417 x 10(-30) esu) and 3 (658 x 10 (-30) esu) are both large, but resonance enhanced. Two-level-corrected nonlinearities for these complexes (124 x 10(-30), 159 x 10(-30) esu, respectively) are also large, despite the presence of electron-donating tert-butyl groups reducing the efficiency of the (formally) electron-accepting quinonal ring in these donor-bridge-acceptor complexes. (C) 2000 Elsevier Science S.A. All rights reserved.
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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