Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges

Bandar Babgi; Luca Rigamonti; Marie P. Cifuentes; T. Christopher Corkery; Michael D. Randles; Torsten Schwich; Simon Petrie; Robert Stranger; Ayele Teshome; Inge Asselberghs; Koen Clays; Marek Samoc; Mark G. Humphrey

doi:10.1021/ja902793z

Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges

Bandar Babgi, Luca Rigamonti, Marie P. Cifuentes, T. Christopher Corkery, Michael D. Randles, Torsten Schwich, Simon Petrie, Robert Stranger, Ayele Teshome, Inge Asselberghs, Koen Clays, Marek Samoc, Mark G. Humphrey

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

86 Citations (Scopus)

Abstract

The syntheses of trans-[Ru{4,4′-C≡CC₆H ₂[2,5-(OEt)₂]C≡CC₆H₄NO ₂}Cl(dppm)₂] (19), trans-[Ru{4,4′,4″- C≡CC₆H₄C≡CC₆H₂[2,5-(OEt) ₂]C≡CC₆H₄NO₂}Cl(dppm) ₂] (20), trans-[Ru{4,4′,4″,4‴-C≡CC ₆H₄C≡CC₆H₂[2,5-(OEt) ₂]C≡CC₆H₂[2,5-(OEt)₂] C≡CC₆H₄NO₂}Cl(dppe)₂] (21), trans-[Ru{4,4′,4′,4‴-C≡CC₆H ₄C≡CC₆H₂[2,5-(OEt)₂] C≡CC₆H₂[2,5-(OEt)₂]C≡CC ₆H₄NO₂}Cl(dppm)₂] (22), trans-[Ru{4,4′,4″,4‴-C≡CC₆H ₄C≡CC₆H₄C≡CC₆H ₂[2,5-(OEt)₂]C≡CC₆H₄NO ₂}Cl(dppm)₂] (23), and trans-[Ru{4,4′,4″, 4‴,4′‴-C≡CC₆H₄C≡CC ₆H₄C≡CC₆H₂[2,5-(OEt) ₂]C≡CC₆H₂[2,5-(OEt)₂] C≡CC₆H₄NO₂}Cl(dppm)₂] (24) are reported, together with those of precursor alkynes, complexes with the donor-π-bridge-acceptor formulation that affords efficient quadratic and cubic NLO compounds; the identity of 19 was confirmed by a structural study. The electrochemical properties of 19-24 and related complexes with shorter π-bridge ligands were assessed by cyclic voltammetry, and the linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties were assayed by UV-vis-NIR spectroscopy, hyper-Rayleigh scattering studies at 1064 and 1300 nm, and broad spectral range femtosecond Z-scan studies, respectively. The Ru^II/III oxidation potentials and wavelengths of the optical absorption maxima decrease on π-bridge lengthening, until the tri(phenyleneethynylene) complex is reached, further chain lengthening leaving these parameters invariant; theoretical studies employing time-dependent density functional theory have shed light on this behavior. The quadratic nonlinearity β₁₀₆₄ and two-photon absorption cross-section reach maximal values at this same π-bridge length, a similar saturation behavior that may reflect a common importance of ruthenium-to-alkynyl ligand charge transfer in electronic and optical behavior in these molecules.

Original language	English
Pages (from-to)	10293-10307
Number of pages	15
Journal	Journal of the American Chemical Society
Volume	131
Issue number	29
DOIs	https://doi.org/10.1021/ja902793z
Publication status	Published - 29 Jul 2009

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Babgi, B., Rigamonti, L., Cifuentes, M. P., Corkery, T. C., Randles, M. D., Schwich, T., Petrie, S., Stranger, R., Teshome, A., Asselberghs, I., Clays, K., Samoc, M., & Humphrey, M. G. (2009). Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges. Journal of the American Chemical Society, 131(29), 10293-10307. https://doi.org/10.1021/ja902793z

Babgi, Bandar ; Rigamonti, Luca ; Cifuentes, Marie P. et al. / Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 29. pp. 10293-10307.

@article{6abf7460f5894d1f9c93206893b1b5de,

title = "Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges",

abstract = "The syntheses of trans-[Ru\{4,4′-C≡CC6H 2[2,5-(OEt)2]C≡CC6H4NO 2\}Cl(dppm)2] (19), trans-[Ru\{4,4′,4″- C≡CC6H4C≡CC6H2[2,5-(OEt) 2]C≡CC6H4NO2\}Cl(dppm) 2] (20), trans-[Ru\{4,4′,4″,4‴-C≡CC 6H4C≡CC6H2[2,5-(OEt) 2]C≡CC6H2[2,5-(OEt)2] C≡CC6H4NO2\}Cl(dppe)2] (21), trans-[Ru\{4,4′,4′,4‴-C≡CC6H 4C≡CC6H2[2,5-(OEt)2] C≡CC6H2[2,5-(OEt)2]C≡CC 6H4NO2\}Cl(dppm)2] (22), trans-[Ru\{4,4′,4″,4‴-C≡CC6H 4C≡CC6H4C≡CC6H 2[2,5-(OEt)2]C≡CC6H4NO 2\}Cl(dppm)2] (23), and trans-[Ru\{4,4′,4″, 4‴,4′‴-C≡CC6H4C≡CC 6H4C≡CC6H2[2,5-(OEt) 2]C≡CC6H2[2,5-(OEt)2] C≡CC6H4NO2\}Cl(dppm)2] (24) are reported, together with those of precursor alkynes, complexes with the donor-π-bridge-acceptor formulation that affords efficient quadratic and cubic NLO compounds; the identity of 19 was confirmed by a structural study. The electrochemical properties of 19-24 and related complexes with shorter π-bridge ligands were assessed by cyclic voltammetry, and the linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties were assayed by UV-vis-NIR spectroscopy, hyper-Rayleigh scattering studies at 1064 and 1300 nm, and broad spectral range femtosecond Z-scan studies, respectively. The RuII/III oxidation potentials and wavelengths of the optical absorption maxima decrease on π-bridge lengthening, until the tri(phenyleneethynylene) complex is reached, further chain lengthening leaving these parameters invariant; theoretical studies employing time-dependent density functional theory have shed light on this behavior. The quadratic nonlinearity β1064 and two-photon absorption cross-section reach maximal values at this same π-bridge length, a similar saturation behavior that may reflect a common importance of ruthenium-to-alkynyl ligand charge transfer in electronic and optical behavior in these molecules.",

author = "Bandar Babgi and Luca Rigamonti and Cifuentes, \{Marie P.\} and Corkery, \{T. Christopher\} and Randles, \{Michael D.\} and Torsten Schwich and Simon Petrie and Robert Stranger and Ayele Teshome and Inge Asselberghs and Koen Clays and Marek Samoc and Humphrey, \{Mark G.\}",

year = "2009",

month = jul,

day = "29",

doi = "10.1021/ja902793z",

language = "English",

volume = "131",

pages = "10293--10307",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "29",

}

Babgi, B, Rigamonti, L, Cifuentes, MP, Corkery, TC, Randles, MD, Schwich, T, Petrie, S, Stranger, R, Teshome, A, Asselberghs, I, Clays, K, Samoc, M & Humphrey, MG 2009, 'Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges', Journal of the American Chemical Society, vol. 131, no. 29, pp. 10293-10307. https://doi.org/10.1021/ja902793z

Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges. / Babgi, Bandar; Rigamonti, Luca; Cifuentes, Marie P. et al.
In: Journal of the American Chemical Society, Vol. 131, No. 29, 29.07.2009, p. 10293-10307.

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

TY - JOUR

T1 - Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges

AU - Babgi, Bandar

AU - Rigamonti, Luca

AU - Cifuentes, Marie P.

AU - Corkery, T. Christopher

AU - Randles, Michael D.

AU - Schwich, Torsten

AU - Petrie, Simon

AU - Stranger, Robert

AU - Teshome, Ayele

AU - Asselberghs, Inge

AU - Clays, Koen

AU - Samoc, Marek

AU - Humphrey, Mark G.

PY - 2009/7/29

Y1 - 2009/7/29

N2 - The syntheses of trans-[Ru{4,4′-C≡CC6H 2[2,5-(OEt)2]C≡CC6H4NO 2}Cl(dppm)2] (19), trans-[Ru{4,4′,4″- C≡CC6H4C≡CC6H2[2,5-(OEt) 2]C≡CC6H4NO2}Cl(dppm) 2] (20), trans-[Ru{4,4′,4″,4‴-C≡CC 6H4C≡CC6H2[2,5-(OEt) 2]C≡CC6H2[2,5-(OEt)2] C≡CC6H4NO2}Cl(dppe)2] (21), trans-[Ru{4,4′,4′,4‴-C≡CC6H 4C≡CC6H2[2,5-(OEt)2] C≡CC6H2[2,5-(OEt)2]C≡CC 6H4NO2}Cl(dppm)2] (22), trans-[Ru{4,4′,4″,4‴-C≡CC6H 4C≡CC6H4C≡CC6H 2[2,5-(OEt)2]C≡CC6H4NO 2}Cl(dppm)2] (23), and trans-[Ru{4,4′,4″, 4‴,4′‴-C≡CC6H4C≡CC 6H4C≡CC6H2[2,5-(OEt) 2]C≡CC6H2[2,5-(OEt)2] C≡CC6H4NO2}Cl(dppm)2] (24) are reported, together with those of precursor alkynes, complexes with the donor-π-bridge-acceptor formulation that affords efficient quadratic and cubic NLO compounds; the identity of 19 was confirmed by a structural study. The electrochemical properties of 19-24 and related complexes with shorter π-bridge ligands were assessed by cyclic voltammetry, and the linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties were assayed by UV-vis-NIR spectroscopy, hyper-Rayleigh scattering studies at 1064 and 1300 nm, and broad spectral range femtosecond Z-scan studies, respectively. The RuII/III oxidation potentials and wavelengths of the optical absorption maxima decrease on π-bridge lengthening, until the tri(phenyleneethynylene) complex is reached, further chain lengthening leaving these parameters invariant; theoretical studies employing time-dependent density functional theory have shed light on this behavior. The quadratic nonlinearity β1064 and two-photon absorption cross-section reach maximal values at this same π-bridge length, a similar saturation behavior that may reflect a common importance of ruthenium-to-alkynyl ligand charge transfer in electronic and optical behavior in these molecules.

AB - The syntheses of trans-[Ru{4,4′-C≡CC6H 2[2,5-(OEt)2]C≡CC6H4NO 2}Cl(dppm)2] (19), trans-[Ru{4,4′,4″- C≡CC6H4C≡CC6H2[2,5-(OEt) 2]C≡CC6H4NO2}Cl(dppm) 2] (20), trans-[Ru{4,4′,4″,4‴-C≡CC 6H4C≡CC6H2[2,5-(OEt) 2]C≡CC6H2[2,5-(OEt)2] C≡CC6H4NO2}Cl(dppe)2] (21), trans-[Ru{4,4′,4′,4‴-C≡CC6H 4C≡CC6H2[2,5-(OEt)2] C≡CC6H2[2,5-(OEt)2]C≡CC 6H4NO2}Cl(dppm)2] (22), trans-[Ru{4,4′,4″,4‴-C≡CC6H 4C≡CC6H4C≡CC6H 2[2,5-(OEt)2]C≡CC6H4NO 2}Cl(dppm)2] (23), and trans-[Ru{4,4′,4″, 4‴,4′‴-C≡CC6H4C≡CC 6H4C≡CC6H2[2,5-(OEt) 2]C≡CC6H2[2,5-(OEt)2] C≡CC6H4NO2}Cl(dppm)2] (24) are reported, together with those of precursor alkynes, complexes with the donor-π-bridge-acceptor formulation that affords efficient quadratic and cubic NLO compounds; the identity of 19 was confirmed by a structural study. The electrochemical properties of 19-24 and related complexes with shorter π-bridge ligands were assessed by cyclic voltammetry, and the linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties were assayed by UV-vis-NIR spectroscopy, hyper-Rayleigh scattering studies at 1064 and 1300 nm, and broad spectral range femtosecond Z-scan studies, respectively. The RuII/III oxidation potentials and wavelengths of the optical absorption maxima decrease on π-bridge lengthening, until the tri(phenyleneethynylene) complex is reached, further chain lengthening leaving these parameters invariant; theoretical studies employing time-dependent density functional theory have shed light on this behavior. The quadratic nonlinearity β1064 and two-photon absorption cross-section reach maximal values at this same π-bridge length, a similar saturation behavior that may reflect a common importance of ruthenium-to-alkynyl ligand charge transfer in electronic and optical behavior in these molecules.

UR - https://www.scopus.com/pages/publications/67651213432

U2 - 10.1021/ja902793z

DO - 10.1021/ja902793z

M3 - Article

SN - 0002-7863

VL - 131

SP - 10293

EP - 10307

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 29

ER -

Babgi B, Rigamonti L, Cifuentes MP, Corkery TC, Randles MD, Schwich T et al. Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges. Journal of the American Chemical Society. 2009 Jul 29;131(29):10293-10307. doi: 10.1021/ja902793z

Length-dependent convergence and saturation behavior of electrochemical, linear optical, quadratic nonlinear optical, and cubic nonlinear optical properties of dipolar alkynylruthenium complexes with oligo(phenyleneethynylene) bridges

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