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Title: Donor-acceptor complexes incorporating ferrocenes: spectroelectrochemical characterisation, quadratic hyperpolarisabilities and the effects of oxidising and reducing agents
Authors: Malaun, M ×
Kowallick, R
McDonagh, AM
Marcaccio, M
Paul, RL
Asselberghs, Inge
Clays, Koen
Persoons, Andre
Bildstein, B
Fiorini, C
Nunzi, JM
Ward, MD
McCleverty, JA #
Issue Date: Jan-2001
Publisher: Royal soc chemistry
Series Title: Journal of the chemical society-dalton transactions issue:20 pages:3025-3038
Abstract: The donor-acceptor complexes [Fe(C5H5){C(5)H(4)QNHM(NO)(Tp(Me,Me))X}] {Tp(Me,Me) = tris(3,5-dimethylpyrazolyl) borate; Q = nothing, M = Mo, X = Cl, Br, I; M = W, X = Cl; Q = C6H4, M = Mo, X = Cl, Br, I; M = W, X = Cl; Q = CH=CHC6H4 or N=NC6H4, M = Mo, X = Cl), which contain 16-valence electron metal nitrosyl centres, [Fe(C5H5){C(5)H(4)QpyMo(NO)(Tp(Me,Me))Cl}] (py = 4-pyridyl; Q = CH=CH, CH=CHCO, N=CH and C6H4CH=CH), [Fe(C5Me4H){C5H4CH=CHpyMo(NO)(Tp(Me,Me))Cl}] and [Fe(C5Me4H)(C(5)Me(4)QpyZ)] {Q = CH=CH or CH=N, Z = Mo(NO)(Tp(Me,Me))Cl or W(CO)(5); Q=2,4-CH=CH(C4H2S) CH=CH, Z = W(CO)(5) or Me+I-}, some of which contain 17-valence electron molybdenum nitrosyl centres, and [Fe(C5Me4H){C5Me4CH=CH(C4H2S) CH=CHpy}], have been characterised electrochemically, by their electronic spectra, and spectroelectrochemically. Hyper-Rayleigh scattering was used to determine the rst hyperpolarisability,, the data showing that (a) is dependent on the metal in the acceptor fragment, (b) beta increased when Cl or Br was replaced by I and (c) beta increased when the number of methyl groups on the cyclopentadienyl rings increased. The beta -values for comparable complexes containing {Mo(NO)(Tp(Me,Me))Cl} and {W(CO)(5)} moieties were similar. Chemical oxidation of the ferrocenyl or chemical reduction of the molybdenum nitrosyl acceptor fragments in selected complexes caused a reduction of between 25% and 100% in the NLO response. X-Ray structural studies of [Fe(C5H5){C5H4NHMo(NO)(Tp(Me,Me))Cl}] (P (1) over bar) and [Fe(C5Me4H){C5Me4CH=CHpyMo(NO)(Tp(Me,Me))Cl}] (P (1) over bar) are reported.
ISSN: 1472-7773
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

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