Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes

Stephanie K. Hurst; Marie P. Cifuentes; Andrew M. McDonagh; Mark G. Humphrey; Marek Samoc; Barry Luther-Davies; Inge Asselberghs; André Persoons

doi:10.1016/S0022-328X(01)01281-5

Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes

Stephanie K. Hurst
, Marie P. Cifuentes
, Andrew M. McDonagh
, Mark G. Humphrey
, Marek Samoc
, Barry Luther-Davies
, Inge Asselberghs
, André Persoons

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

98 Scopus citations

Abstract

The complexes [Au(4-CCC₆H₄NO₂)(L)] [L=PCy₃ (1), PMe₃ (2)], [(L)Au(μ-4-CCRCC)Au(L)] [R=C₆H₄, L=PCy₃ (4), PPh₃ (5); R=C₆H₄-4-C₆H₄, L=PCy₃ (7), PPh₃ (8)], trans,trans-[RuCl(dppm)₂(μ-4,4′-CCC₆H₄C₆H₄CC)RuCl(dppm)₂] (11), trans-[Ru(X)(Y)(dppe)₂] [X=Cl, Y=4-CCC₆H₄I (12), 4-CCC₆H₄CCSiMe₃ (13); X=CCPh, 4-CCC₆H₄CCH (14)] and {trans-[Ru(CCPh)(dppe)₂]}₂(μ-4,4′-CCC₆H₄CCCCC₆H₄CC) (15) have been prepared and their electrochemical (Ru complexes) and nonlinear optical properties assessed. Electronic communication between the metal centers in 10, 11 and 15 diminishes as the π-delocalizable bridge is lengthened. Quadratic nonlinear optical (NLO) merit increases on replacing triarylphosphine by trialkylphosphine, the relative β values Au(4-CCC₆H₄NO₂)(PPh₃)<1<3 being observed. Cubic NLO values are small for the gold complexes and much larger for the ruthenium examples. Complex 15 has the largest σ₂/MWt (two-photon absorption cross-section/molecular weight) value observed thus far for an organometallic complex.

Original language	English (US)
Pages (from-to)	259-267
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	642
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(01)01281-5
State	Published - 2002

Keywords

Acetylide
Electrochemistry
Gold
Hyperpolarizability
Nonlinear optics
Ruthenium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0022-328X(01)01281-5

Cite this

Hurst, S. K., Cifuentes, M. P., McDonagh, A. M., Humphrey, M. G., Samoc, M., Luther-Davies, B., Asselberghs, I., & Persoons, A. (2002). Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes. Journal of Organometallic Chemistry, 642(1-2), 259-267. https://doi.org/10.1016/S0022-328X(01)01281-5

Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes. / Hurst, Stephanie K.; Cifuentes, Marie P.; McDonagh, Andrew M. et al.
In: Journal of Organometallic Chemistry, Vol. 642, No. 1-2, 2002, p. 259-267.

Research output: Contribution to journal › Article › peer-review

Hurst, SK, Cifuentes, MP, McDonagh, AM, Humphrey, MG, Samoc, M, Luther-Davies, B, Asselberghs, I & Persoons, A 2002, 'Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes', Journal of Organometallic Chemistry, vol. 642, no. 1-2, pp. 259-267. https://doi.org/10.1016/S0022-328X(01)01281-5

@article{fc90239cc3fe4de883b4af67f2bca45b,

title = "Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes",

abstract = "The complexes [Au(4-CCC6H4NO2)(L)] [L=PCy3 (1), PMe3 (2)], [(L)Au(μ-4-CCRCC)Au(L)] [R=C6H4, L=PCy3 (4), PPh3 (5); R=C6H4-4-C6H4, L=PCy3 (7), PPh3 (8)], trans,trans-[RuCl(dppm)2(μ-4,4′-CCC6H4C6H4CC)RuCl(dppm)2] (11), trans-[Ru(X)(Y)(dppe)2] [X=Cl, Y=4-CCC6H4I (12), 4-CCC6H4CCSiMe3 (13); X=CCPh, 4-CCC6H4CCH (14)] and \{trans-[Ru(CCPh)(dppe)2]\}2(μ-4,4′-CCC6H4CCCCC6H4CC) (15) have been prepared and their electrochemical (Ru complexes) and nonlinear optical properties assessed. Electronic communication between the metal centers in 10, 11 and 15 diminishes as the π-delocalizable bridge is lengthened. Quadratic nonlinear optical (NLO) merit increases on replacing triarylphosphine by trialkylphosphine, the relative β values Au(4-CCC6H4NO2)(PPh3)<1<3 being observed. Cubic NLO values are small for the gold complexes and much larger for the ruthenium examples. Complex 15 has the largest σ2/MWt (two-photon absorption cross-section/molecular weight) value observed thus far for an organometallic complex.",

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

author = "Hurst, \{Stephanie K.\} and Cifuentes, \{Marie P.\} and McDonagh, \{Andrew M.\} and Humphrey, \{Mark G.\} and Marek Samoc and Barry Luther-Davies and Inge Asselberghs and Andr{\'e} Persoons",

note = "Funding Information: We thank the Australian Research Council (M.G.H.), the Belgian Government (Grant No. IUAP-PIV/11) (A.P.), the Fund for Scientific Research-Flanders (G.0338.98, G.0407.98) (A.P.), the K.U. Leuven (GOA/2000/03) (A.P.) for support of this work, and Johnson-Matthey Technology Centre (M.G.H.) for the generous loan of ruthenium salts. M.P.C. held an ARC Australian Postdoctoral Research Fellowship, A.M.M. held an Australian Postgraduate Award, and M.G.H. holds an ARC Australian Senior Research Fellowship.",

year = "2002",

doi = "10.1016/S0022-328X(01)01281-5",

language = "English (US)",

volume = "642",

pages = "259--267",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

TY - JOUR

T1 - Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes

AU - Hurst, Stephanie K.

AU - Cifuentes, Marie P.

AU - McDonagh, Andrew M.

AU - Humphrey, Mark G.

AU - Samoc, Marek

AU - Luther-Davies, Barry

AU - Asselberghs, Inge

AU - Persoons, André

N1 - Funding Information: We thank the Australian Research Council (M.G.H.), the Belgian Government (Grant No. IUAP-PIV/11) (A.P.), the Fund for Scientific Research-Flanders (G.0338.98, G.0407.98) (A.P.), the K.U. Leuven (GOA/2000/03) (A.P.) for support of this work, and Johnson-Matthey Technology Centre (M.G.H.) for the generous loan of ruthenium salts. M.P.C. held an ARC Australian Postdoctoral Research Fellowship, A.M.M. held an Australian Postgraduate Award, and M.G.H. holds an ARC Australian Senior Research Fellowship.

PY - 2002

Y1 - 2002

N2 - The complexes [Au(4-CCC6H4NO2)(L)] [L=PCy3 (1), PMe3 (2)], [(L)Au(μ-4-CCRCC)Au(L)] [R=C6H4, L=PCy3 (4), PPh3 (5); R=C6H4-4-C6H4, L=PCy3 (7), PPh3 (8)], trans,trans-[RuCl(dppm)2(μ-4,4′-CCC6H4C6H4CC)RuCl(dppm)2] (11), trans-[Ru(X)(Y)(dppe)2] [X=Cl, Y=4-CCC6H4I (12), 4-CCC6H4CCSiMe3 (13); X=CCPh, 4-CCC6H4CCH (14)] and {trans-[Ru(CCPh)(dppe)2]}2(μ-4,4′-CCC6H4CCCCC6H4CC) (15) have been prepared and their electrochemical (Ru complexes) and nonlinear optical properties assessed. Electronic communication between the metal centers in 10, 11 and 15 diminishes as the π-delocalizable bridge is lengthened. Quadratic nonlinear optical (NLO) merit increases on replacing triarylphosphine by trialkylphosphine, the relative β values Au(4-CCC6H4NO2)(PPh3)<1<3 being observed. Cubic NLO values are small for the gold complexes and much larger for the ruthenium examples. Complex 15 has the largest σ2/MWt (two-photon absorption cross-section/molecular weight) value observed thus far for an organometallic complex.

AB - The complexes [Au(4-CCC6H4NO2)(L)] [L=PCy3 (1), PMe3 (2)], [(L)Au(μ-4-CCRCC)Au(L)] [R=C6H4, L=PCy3 (4), PPh3 (5); R=C6H4-4-C6H4, L=PCy3 (7), PPh3 (8)], trans,trans-[RuCl(dppm)2(μ-4,4′-CCC6H4C6H4CC)RuCl(dppm)2] (11), trans-[Ru(X)(Y)(dppe)2] [X=Cl, Y=4-CCC6H4I (12), 4-CCC6H4CCSiMe3 (13); X=CCPh, 4-CCC6H4CCH (14)] and {trans-[Ru(CCPh)(dppe)2]}2(μ-4,4′-CCC6H4CCCCC6H4CC) (15) have been prepared and their electrochemical (Ru complexes) and nonlinear optical properties assessed. Electronic communication between the metal centers in 10, 11 and 15 diminishes as the π-delocalizable bridge is lengthened. Quadratic nonlinear optical (NLO) merit increases on replacing triarylphosphine by trialkylphosphine, the relative β values Au(4-CCC6H4NO2)(PPh3)<1<3 being observed. Cubic NLO values are small for the gold complexes and much larger for the ruthenium examples. Complex 15 has the largest σ2/MWt (two-photon absorption cross-section/molecular weight) value observed thus far for an organometallic complex.

KW - Acetylide

KW - Electrochemistry

KW - Gold

KW - Hyperpolarizability

KW - Nonlinear optics

KW - Ruthenium

UR - https://www.scopus.com/pages/publications/0000258919

UR - https://www.scopus.com/pages/publications/0000258919#tab=citedBy

U2 - 10.1016/S0022-328X(01)01281-5

DO - 10.1016/S0022-328X(01)01281-5

M3 - Article

AN - SCOPUS:0000258919

SN - 0022-328X

VL - 642

SP - 259

EP - 267

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Organometallic complexes for nonlinear optics. Part 25. Quadratic and cubic hyperpolarizabilities of some dipolar and quadrupolar gold and ruthenium complexes

Abstract

Keywords

ASJC Scopus subject areas

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