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

Malaun, M; Kowallick, R; McDonagh, AM; Marcaccio, M; Paul, RL; Asselberghs, I; Clays, K; Persoons, A; Bildstein, B; Fiorini, C; Nunzi, JM; Ward, MD; McCleverty, JA

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

Malaun, M Kowallick, R McDonagh, AM

Marcaccio, M Paul, RL Asselberghs, I Clays, K Persoons, A Bildstein, B Fiorini, C Nunzi, JM Ward, MD McCleverty, JA

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Publication Type:: Journal Article
Citation:: Journal of the Chemical Society, Dalton Transactions, 2001, (20), pp. 3025 - 3038
Issue Date:: 2001-11-21

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Field	Value	Language
dc.contributor.author	Malaun, M	en_US
dc.contributor.author	Kowallick, R	en_US
dc.contributor.author	McDonagh, AM https://orcid.org/0000-0002-9502-1175	en_US
dc.contributor.author	Marcaccio, M	en_US
dc.contributor.author	Paul, RL	en_US
dc.contributor.author	Asselberghs, I	en_US
dc.contributor.author	Clays, K	en_US
dc.contributor.author	Persoons, A	en_US
dc.contributor.author	Bildstein, B	en_US
dc.contributor.author	Fiorini, C	en_US
dc.contributor.author	Nunzi, JM	en_US
dc.contributor.author	Ward, MD	en_US
dc.contributor.author	McCleverty, JA	en_US
dc.date.issued	2001-11-21	en_US
dc.identifier.citation	Journal of the Chemical Society, Dalton Transactions, 2001, (20), pp. 3025 - 3038	en_US
dc.identifier.issn	1470-479X	en_US
dc.identifier.uri	http://hdl.handle.net/10453/8449
dc.description.abstract	The donor-acceptor complexes [Fe(C5H5){C5H4QNHM(NO)(Tp Me,Me)X}] {TpMe,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){C5H4QpyMo(NO)(Tp Me,Me)Cl}] (py = 4-pyridyl; Q = CH=CH, CH=CHCO, N=CH and C6H4CH=CH), [Fe(C5Me4H){C5H4CH=CHpyMo(NO) (TpMe,Me)Cl}] and [Fe(C5Me4H)(C5Me4QpyZ)] {Q = CH=CH or CH=N, Z = Mo(NO)(TpMe,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(C 4H2S)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)(TpMe,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}] (P1̄) and [Fe(C5Me4H){C5Me4CH=CHpyMo(NO) (TpMe,Me)Cl}] (P1̄) are reported.	en_US
dc.relation.ispartof	Journal of the Chemical Society, Dalton Transactions	en_US
dc.subject.classification	Inorganic & Nuclear Chemistry	en_US
dc.title	Donor-acceptor complexes incorporating ferrocenes: Spectroelectrochemical characterisation, quadratic hyperpolarisabilities and the effects of oxidising and reducing agents	en_US
dc.type	Journal Article
utslib.citation.volume	20	en_US
utslib.for	1007 Nanotechnology	en_US
utslib.for	0306 Physical Chemistry (incl. Structural)	en_US
utslib.for	0302 Inorganic Chemistry	en_US
utslib.for	0307 Theoretical and Computational Chemistry	en_US
utslib.for	0399 Other Chemical Sciences	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
pubs.organisational-group	/University of Technology Sydney/Strength - CCET - Centre for Clean Energy Technology
utslib.copyright.status	closed_access
pubs.issue	20	en_US
pubs.publication-status	Published	en_US

Abstract:

The donor-acceptor complexes [Fe(C5H5){C5H4QNHM(NO)(Tp Me,Me)X}] {TpMe,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){C5H4QpyMo(NO)(Tp Me,Me)Cl}] (py = 4-pyridyl; Q = CH=CH, CH=CHCO, N=CH and C6H4CH=CH), [Fe(C5Me4H){C5H4CH=CHpyMo(NO) (TpMe,Me)Cl}] and [Fe(C5Me4H)(C5Me4QpyZ)] {Q = CH=CH or CH=N, Z = Mo(NO)(TpMe,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(C 4H2S)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)(TpMe,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}] (P1̄) and [Fe(C5Me4H){C5Me4CH=CHpyMo(NO) (TpMe,Me)Cl}] (P1̄) are reported.

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