Organometallic complexes for nonlinear optics: Part 31. Cubic hyperpolarizabilities of ferrocenyl-linked gold and ruthenium complexes

Stephanie K. Hurst; Mark G. Humphrey; Joseph P. Morrall; Marie P. Cifuentes; Marek Samoc; Barry Luther-Davies; Graham A. Heath; Anthony C. Willis

doi:10.1016/S0022-328X(02)02131-9

Organometallic complexes for nonlinear optics: Part 31. Cubic hyperpolarizabilities of ferrocenyl-linked gold and ruthenium complexes

Stephanie K. Hurst, Mark G. Humphrey^*, Joseph P. Morrall, Marie P. Cifuentes, Marek Samoc, Barry Luther-Davies, Graham A. Heath, Anthony C. Willis

^*Corresponding author for this work

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Abstract

The complexes [Fe{η-C ₅ H ₄ -(E)-CH= CH-4-C ₆ H ₄ C≡CX} ₂ ] [X=SiMe ₃ (1), H (2), Au(PCy ₃ ) (3), Au(PPh ₃ ) (4), Au(PMe ₃ ) (5), RuCl(dppm) ₂ (7), RuCl(dppe) ₂ (8)] and [Fe{η-C ₅ H ₄ -(E)-CH= CH-4-C ₆ H ₄ CH≡CRuCl} (dppm) ₂ } ₂ ](PF ₆ ) ₂ (6) have been prepared and the identities of 1 and 7 confirmed by single-crystal X-ray structural studies. Complexes 1-8 exhibit reversible oxidation waves in their cyclic voltammograms attributed to the Fe ^II/III couple of the ferrocenyl groups, 6-8 also showing reversible (7, 8) or nonreversible (6) processes attributed to Ru-centered oxidation. Cubic nonlinearities at 800 nm by the Z-scan method are low for 1-5; in contrast, complexes 6 and 7 exhibit large negative γ _real and large γ _imag values. A factor of 4 difference in γ and two-photon absorption cross-section σ ₂ values for 6 and 7 suggest that they have potential as protically switchable NLO materials.

Original language	English
Pages (from-to)	56-65
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	670
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(02)02131-9
Publication status	Published - 17 Mar 2003

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@article{fd9b2a7c8ad2486ba7ca5eb076e45e13,

title = "Organometallic complexes for nonlinear optics: Part 31. Cubic hyperpolarizabilities of ferrocenyl-linked gold and ruthenium complexes",

abstract = " The complexes [Fe{η-C 5 H 4 -(E)-CH= CH-4-C 6 H 4 C≡CX} 2 ] [X=SiMe 3 (1), H (2), Au(PCy 3 ) (3), Au(PPh 3 ) (4), Au(PMe 3 ) (5), RuCl(dppm) 2 (7), RuCl(dppe) 2 (8)] and [Fe{η-C 5 H 4 -(E)-CH= CH-4-C 6 H 4 CH≡CRuCl} (dppm) 2 } 2 ](PF 6 ) 2 (6) have been prepared and the identities of 1 and 7 confirmed by single-crystal X-ray structural studies. Complexes 1-8 exhibit reversible oxidation waves in their cyclic voltammograms attributed to the Fe II/III couple of the ferrocenyl groups, 6-8 also showing reversible (7, 8) or nonreversible (6) processes attributed to Ru-centered oxidation. Cubic nonlinearities at 800 nm by the Z-scan method are low for 1-5; in contrast, complexes 6 and 7 exhibit large negative γ real and large γ imag values. A factor of 4 difference in γ and two-photon absorption cross-section σ 2 values for 6 and 7 suggest that they have potential as protically switchable NLO materials.",

keywords = "Acetylide, Electrochemistry, Gold, Hyperpolarizability, Iron, Nonlinear optics, Ruthenium",

author = "Hurst, {Stephanie K.} and Humphrey, {Mark G.} and Morrall, {Joseph P.} and Cifuentes, {Marie P.} and Marek Samoc and Barry Luther-Davies and Heath, {Graham A.} and Willis, {Anthony C.}",

year = "2003",

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doi = "10.1016/S0022-328X(02)02131-9",

language = "English",

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pages = "56--65",

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issn = "0022-328X",

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TY - JOUR

T1 - Organometallic complexes for nonlinear optics

T2 - Part 31. Cubic hyperpolarizabilities of ferrocenyl-linked gold and ruthenium complexes

AU - Hurst, Stephanie K.

AU - Humphrey, Mark G.

AU - Morrall, Joseph P.

AU - Cifuentes, Marie P.

AU - Samoc, Marek

AU - Luther-Davies, Barry

AU - Heath, Graham A.

AU - Willis, Anthony C.

PY - 2003/3/17

Y1 - 2003/3/17

N2 - The complexes [Fe{η-C 5 H 4 -(E)-CH= CH-4-C 6 H 4 C≡CX} 2 ] [X=SiMe 3 (1), H (2), Au(PCy 3 ) (3), Au(PPh 3 ) (4), Au(PMe 3 ) (5), RuCl(dppm) 2 (7), RuCl(dppe) 2 (8)] and [Fe{η-C 5 H 4 -(E)-CH= CH-4-C 6 H 4 CH≡CRuCl} (dppm) 2 } 2 ](PF 6 ) 2 (6) have been prepared and the identities of 1 and 7 confirmed by single-crystal X-ray structural studies. Complexes 1-8 exhibit reversible oxidation waves in their cyclic voltammograms attributed to the Fe II/III couple of the ferrocenyl groups, 6-8 also showing reversible (7, 8) or nonreversible (6) processes attributed to Ru-centered oxidation. Cubic nonlinearities at 800 nm by the Z-scan method are low for 1-5; in contrast, complexes 6 and 7 exhibit large negative γ real and large γ imag values. A factor of 4 difference in γ and two-photon absorption cross-section σ 2 values for 6 and 7 suggest that they have potential as protically switchable NLO materials.

AB - The complexes [Fe{η-C 5 H 4 -(E)-CH= CH-4-C 6 H 4 C≡CX} 2 ] [X=SiMe 3 (1), H (2), Au(PCy 3 ) (3), Au(PPh 3 ) (4), Au(PMe 3 ) (5), RuCl(dppm) 2 (7), RuCl(dppe) 2 (8)] and [Fe{η-C 5 H 4 -(E)-CH= CH-4-C 6 H 4 CH≡CRuCl} (dppm) 2 } 2 ](PF 6 ) 2 (6) have been prepared and the identities of 1 and 7 confirmed by single-crystal X-ray structural studies. Complexes 1-8 exhibit reversible oxidation waves in their cyclic voltammograms attributed to the Fe II/III couple of the ferrocenyl groups, 6-8 also showing reversible (7, 8) or nonreversible (6) processes attributed to Ru-centered oxidation. Cubic nonlinearities at 800 nm by the Z-scan method are low for 1-5; in contrast, complexes 6 and 7 exhibit large negative γ real and large γ imag values. A factor of 4 difference in γ and two-photon absorption cross-section σ 2 values for 6 and 7 suggest that they have potential as protically switchable NLO materials.

KW - Acetylide

KW - Electrochemistry

KW - Gold

KW - Hyperpolarizability

KW - Iron

KW - Nonlinear optics

KW - Ruthenium

UR - http://www.scopus.com/inward/record.url?scp=0037451009&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(02)02131-9

DO - 10.1016/S0022-328X(02)02131-9

M3 - Article

SN - 0022-328X

VL - 670

SP - 56

EP - 65

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Organometallic complexes for nonlinear optics: Part 31. Cubic hyperpolarizabilities of ferrocenyl-linked gold and ruthenium complexes

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