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Title: Synthesis and second-order nonlinear optical properties of donor-acceptor sigma-alkynyl and sigma-enynyl indenylruthenium(II) complexes. X-ray crystal structures of [Ru{C CCH=C(C6H4NO2-3)(2)}(eta(5)-C9H7)(PPh3)(2)] and (EE)-[Ru{C C(CH=CH)(2)-C6H4NO2-4}(eta(5)-C9H7)(PPh3)(2)]
Authors: Cadierno, V ×
Conejero, S
Gamasa, MP
Gimeno, J
Asselberghs, Inge
Houbrechts, Stephan
Clays, Koen
Persoons, Andre
Borge, J
Garcia-Granda, S #
Issue Date: Jan-1999
Publisher: Amer chemical soc
Series Title: Organometallics vol:18 issue:4 pages:582-597
Abstract: sigma-Alkynyl complexes [Ru(C equivalent to C-C6H4R-4)(eta(5)-C9H7)L-2] (L = PPh3, R = NO2 (3a), C equivalent to C-C6H4- NO2-4 (4), N=CH-C6H4NO2-4 (5); L-2= 1,2-bis(diphenylphosphino)ethane (dppe), R=NO2(3b); L-2 = bis(diphenylphosphino)methane (dppm), R = NO2 (3c)) have been prepared by reaction of [RuCl(eta(5)-C9H7)L-2] (1a-c) with HC equivalent to C-C6H4R-4 and NaPF6, via deprotonation of the corresponding intermediate vinylidene derivatives. The treatment of the alkynyl-phosphonio complex [Ru{C equivalent to CCH2(PPh3)}(eta(5)-C9H7)(PPh3)(2)][PF6] (6) with (LiBu)-Bu-n and the appropriate aldehyde or ketone yields, via Wittig type reactions, sigma-enynyl complexes [Ru{C equivalent to CCH=CR1(CH=CH)(n)R-2}(eta(5)-C9H7)(PPh3)(2)] (n = 0, R-1= H, R-2 = C6H4NO2-4 (7a), C4H2ONO2-3,4 (8a), C4H2SNO2-3,4 (8b), C6H4CN-4 (13), C5H4N-4 (16); n = 0, R-1= R-2 = C6H4NO2-3 (9); n = 1, R-1 = H, R-2 = C6H4NO2-4 (7b)) isolated as mixtures of the corresponding E and Z stereoisomers. The structures of complexes 7b and 9 have been confirmed by X-ray diffraction. Structural data in the solid state as well as in solution (C-13{H-1} NMR) show an extensive electronic delocalization between the donor fragment [Ru(eta(5)-C9H7)(PPh3)(2)] and the acceptor nitroaryl group. In accordance with this, values of resonantly enhanced molecular quadratic hyperpolarizabilities (beta) for these donor-acceptor derivatives (beta(1064) (nm)= 100-1320 x 10(-30) esu), determined by the hyper-Rayleigh scattering technique (HRS) at 1064 nm which are dependent on the molecular design of the bridged enynyl chain, are significantly larger than those of their analogous organic chromophores. Mixed-valence bimetallic donor-acceptor derivatives [(eta(5)-C9H7)(PPh3)(2)Ru{(mu-C equivalent to N)ML5}][CF3SO3](n) (n = 0, ML5 = Cr(CO)(5) (11a), W(CO)(5) (11b); n = 3, ML5 = Ru(NH3)(5) (12)), [(eta(5)-C9H7)(PPh3)(2)Ru{(mu-C equivalent to CCH=CH-C6H4C equivalent to N-4)ML5}][CF3SO3](n) (n = 0, ML5 = Cr(CO)(5) )[(E, Z)-14a], W(CO)(5) [(E, Z)-14b]; n = 3, ML5 = Ru(NH3)(5) [(E, 2)-15] and [(eta(5)-C9H7)(PPh3)(2)Ru{(mu-C equivalent to CCH=CH-C5H4N-4)M(CO)(5)}] (M = Cr [(E)-17a], W [(E)-17b]) have also been prepared in high yields. Static quadratic hyperpolarizabilities values of these derivatives (beta(o) = 10-150 x 10(-30) esu) surpass the largest reported to date for bimetallic compounds.
ISSN: 0276-7333
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

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