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Donor–acceptor complexes incorporating ferrocenes: spectroelectrochemical characterisation, quadratic hyperpolarisabilities and the effects of oxidising and reducing agents

Michael Malaun, Ralph Kowallick, Andrew M. McDonagh, Massimo Marcaccio, Rowena L. Paul, Inge Asselberghs, Koen Clays, André Persoons, Benno Bildstein, Céline Fiorini, Jean-Michel Nunzi, Michael D. Ward (+1 others)
2001 Journal of the Chemical Society. Dalton Transactions  

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Cl), which contain 16-valence electron metal nitrosyl centres, [Fe(C 5 H 5 ){C 5 H 4 QpyMo(NO)(Tp Me,Me )Cl}] (py = 4-pyridyl; Q = CH᎐ ᎐ CH, CH᎐ ᎐ CHCO, N᎐ ᎐ CH and C 6 H 4 CH᎐ ᎐ CH), [Fe(C 5 Me 4 H){C 5 H 4 CH᎐ ᎐ CHpyMo(NO)(Tp Me,Me )Cl}] and [Fe(C 5 Me 4 H)(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(C 4 H 2 S)CH᎐ ᎐ CH, Z = W(CO) 5 or Me ϩ I Ϫ }, some of which contain 17-valence electron molybdenum nitrosyl centres, and [Fe(C 5 Me 4 H){C 5
more » ... e 4 CH᎐ ᎐ CH(C 4 H 2 S)CH᎐ ᎐ CHpy}], have been characterised electrochemically, by their electronic spectra, and spectroelectrochemically. Hyper-Rayleigh scattering was used to determine the first hyperpolarisability, β, the data showing that (a) β is dependent on the metal in the acceptor fragment, (b) β increased when Cl or Br was replaced by I and (c) β increased when the number of methyl groups on the cyclopentadienyl rings increased. The β-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(C 5 H 5 ){C 5 H 4 NHMo(NO)(Tp Me,Me )Cl}] (P1) and [Fe(C 5 Me 4 H){C 5 Me 4 CH᎐ ᎐ CHpyMo(NO)(Tp Me,Me )Cl}] (P1) are reported. DALTON
doi:10.1039/b104791b fatcat:ae2rnmduwbdijkcvglxz7cwyoy
Citation

Michael Malaun, Ralph Kowallick, Andrew M. McDonagh, Massimo Marcaccio, Rowena L. Paul, Inge Asselberghs, Koen Clays, André Persoons, Benno Bildstein, Céline Fiorini, Jean-Michel Nunzi, Michael D. Ward, Jon A. McCleverty. "Donor–acceptor complexes incorporating ferrocenes: spectroelectrochemical characterisation, quadratic hyperpolarisabilities and the effects of oxidising and reducing agents." Journal of the Chemical Society. Dalton Transactions (2001) 3025-3038