Title: Organometallic complexes for nonlinear optics Part 21. Syntheses and quadratic hyperpolarizabilities of alkynyl complexes containing optically active 1,2-bis(methylphenylphosphino)benzene ligands
Authors: McDonagh, AM
Cifuentes, MP
Humphrey, MG
Houbrechts, Stephan
Maes, J
Persoons, Andre
Samoc, M
Luther-Davies, B #
Issue Date: Jan-2000
Publisher: Elsevier science sa
Series Title: Journal of Organometallic Chemistry vol:610 issue:1-2 pages:71-79
Abstract: The preparation of the chloro complex trans-[FeCl2{(R,R)-diph}(2)] (1) and the alkynyl complexes trans-[M(4-C=CC6H4R)Cl{(R,R)-diph}(2)] [M=Fe, R=NO2 (2); M=Ru, R=H (4) NO, (5), (E)-CH=CH-4-C6H4NO2 (6); M=Os, R=NO2 (7)], incorporating the optically active diphosphine 1,2-bis(methylphenylphosphino)benzene (diph), are described. Oxidation potentials, as determined by cyclic voltammetry, increase as 2 < 7 < 5. Molecular quadratic nonlinearities by hyper-Rayleigh scattering at 1064 nm increase upon introduction of an acceptor group (4 < 5), chain-lengthening of bridging group (5 < 6), and proceeding from 3d to 4d and 5d metal (2 less than or equal to 5 less than or equal to 7). Two-level-corrected nonlinearities reproduce the first two trends, but metal variation follows the sequence 2 < 7 < 5. The experimental and two-level-corrected nonlinearities for 6 (2795 x 10(-30) and 406 x 10(-30) esu, respectively), are amongst the largest observed thus far for organometallic complexes. Crystals of complexes 2 and 7 exhibit second-harmonic generation (assessed using the Kurtz powder technique), with an efficiency for the former of twice that of urea. (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
# (joint) last author

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