Organometallic complexes for nonlinear optics. 43. Quadratic optical nonlinearities of dipolar alkynylruthenium complexes with phenyleneethynylene/ phenylenevinylene bridges

Luca Rigamonti; Bandar Babgi; Marie P. Cifuentes; Rachel L. Roberts; Simon Petrie; Robert Stranger; Stefania Righetto; Ayele Teshome; Inge Asselberghs; Koen Clays; Mark G. Humphrey

doi:10.1021/ic801953z

Organometallic complexes for nonlinear optics. 43. Quadratic optical nonlinearities of dipolar alkynylruthenium complexes with phenyleneethynylene/ phenylenevinylene bridges

Luca Rigamonti, Bandar Babgi, Marie P. Cifuentes, Rachel L. Roberts, Simon Petrie, Robert Stranger, Stefania Righetto, Ayele Teshome, Inge Asselberghs, Koen Clays, Mark G. Humphrey

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

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Abstract

The syntheses of trans-[Ru(4,4′-C≡CC₆H ₄C≡CC₆H₄NO₂)Cl(dppe) ₂] (19) and the systematically varied complexes trans-[Ru(4,4′, 4′′-C≡CC₆H₄X₂C ₆H₄Y₂C₆H₄NO ₂)Cl(L₂)₂] [L₂ = dppe, X₂ = C≡C, Y₂ = (E)-CH=CH (12), C≡C (18); L₂ = dppe, X₂ = (E)-CH)CH, Y₂ = C≡C (14), (E)-CH)CH (16); L₂ = dppm, X₂ = C≡C, Y₂ = (E)-CH)CH (13); L₂ = dppm, X₂ = (E)-CH=CH, Y₂ = C≡C (15), (E)-CH)CH (17)] are reported, the latter being donorbridge- acceptor complexes varying in bridge composition by replacement of yne with E-ene linkages, together with their cyclic voltammetric data, linear optical, and quadratic nonlinear optical response data. Ru^II/III oxidation potentials increase on replacing yne linkage by E-ene linkage at the phenylene adjacent to the metal center, and on replacing dppe by dppm co-ligands. The low-energy optical absorption maxima occur in the region 20400-23300 cm ^-1 and are metal-to-ligand charge-transfer (MLCT) in origin; these bands undergo a blue-shift upon π-bridge lengthening by addition of phenyleneethynylene units, and on replacing E-ene linkages by yne linkages. Time-dependent density functional theory calculations on model complexes have suggested assignments for the low-energy bands. The optical spectra of selected oxidized species contain low-energy ligand-to-metal charge transfer (LMCT) bands centered in the region 9760-11800 cm^-1. Quadratic molecular nonlinearities from hyper-Rayleigh scattering (HRS) studies at 1064 nm reveal an increase in the two-level-corrected β₀ value on π-bridge lengthening, a trend that is not seen with β values because of the blue-shift in λ_max for this structural modification. Replacing yne linkages by E-ene linkage at the phenylene adjacent to the metal center or dppm co-ligand by dppe results in an increase in β and β₀ values. In contrast, quadratic molecular nonlinearities by HRS at 1300 nm or electric field-induced secondharmonic generation (EFISH) studies at 1907 nm do not afford clear trends.

Original language	English
Pages (from-to)	3562-3572
Number of pages	11
Journal	Inorganic Chemistry
Volume	48
Issue number	8
DOIs	https://doi.org/10.1021/ic801953z
Publication status	Published - 20 Apr 2009

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Rigamonti, L., Babgi, B., Cifuentes, M. P., Roberts, R. L., Petrie, S., Stranger, R., Righetto, S., Teshome, A., Asselberghs, I., Clays, K., & Humphrey, M. G. (2009). Organometallic complexes for nonlinear optics. 43. Quadratic optical nonlinearities of dipolar alkynylruthenium complexes with phenyleneethynylene/ phenylenevinylene bridges. Inorganic Chemistry, 48(8), 3562-3572. https://doi.org/10.1021/ic801953z

@article{5888bc1626224047a370efc4e581a58c,

title = "Organometallic complexes for nonlinear optics. 43. Quadratic optical nonlinearities of dipolar alkynylruthenium complexes with phenyleneethynylene/ phenylenevinylene bridges",

abstract = "The syntheses of trans-[Ru(4,4′-C≡CC6H 4C≡CC6H4NO2)Cl(dppe) 2] (19) and the systematically varied complexes trans-[Ru(4,4′, 4′′-C≡CC6H4X2C 6H4Y2C6H4NO 2)Cl(L2)2] [L2 = dppe, X2 = C≡C, Y2 = (E)-CH=CH (12), C≡C (18); L2 = dppe, X2 = (E)-CH)CH, Y2 = C≡C (14), (E)-CH)CH (16); L2 = dppm, X2 = C≡C, Y2 = (E)-CH)CH (13); L2 = dppm, X2 = (E)-CH=CH, Y2 = C≡C (15), (E)-CH)CH (17)] are reported, the latter being donorbridge- acceptor complexes varying in bridge composition by replacement of yne with E-ene linkages, together with their cyclic voltammetric data, linear optical, and quadratic nonlinear optical response data. RuII/III oxidation potentials increase on replacing yne linkage by E-ene linkage at the phenylene adjacent to the metal center, and on replacing dppe by dppm co-ligands. The low-energy optical absorption maxima occur in the region 20400-23300 cm -1 and are metal-to-ligand charge-transfer (MLCT) in origin; these bands undergo a blue-shift upon π-bridge lengthening by addition of phenyleneethynylene units, and on replacing E-ene linkages by yne linkages. Time-dependent density functional theory calculations on model complexes have suggested assignments for the low-energy bands. The optical spectra of selected oxidized species contain low-energy ligand-to-metal charge transfer (LMCT) bands centered in the region 9760-11800 cm-1. Quadratic molecular nonlinearities from hyper-Rayleigh scattering (HRS) studies at 1064 nm reveal an increase in the two-level-corrected β0 value on π-bridge lengthening, a trend that is not seen with β values because of the blue-shift in λmax for this structural modification. Replacing yne linkages by E-ene linkage at the phenylene adjacent to the metal center or dppm co-ligand by dppe results in an increase in β and β0 values. In contrast, quadratic molecular nonlinearities by HRS at 1300 nm or electric field-induced secondharmonic generation (EFISH) studies at 1907 nm do not afford clear trends.",

author = "Luca Rigamonti and Bandar Babgi and Cifuentes, \{Marie P.\} and Roberts, \{Rachel L.\} and Simon Petrie and Robert Stranger and Stefania Righetto and Ayele Teshome and Inge Asselberghs and Koen Clays and Humphrey, \{Mark G.\}",

year = "2009",

month = apr,

day = "20",

doi = "10.1021/ic801953z",

language = "English",

volume = "48",

pages = "3562--3572",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "8",

}

Rigamonti, L, Babgi, B, Cifuentes, MP, Roberts, RL, Petrie, S, Stranger, R, Righetto, S, Teshome, A, Asselberghs, I, Clays, K & Humphrey, MG 2009, 'Organometallic complexes for nonlinear optics. 43. Quadratic optical nonlinearities of dipolar alkynylruthenium complexes with phenyleneethynylene/ phenylenevinylene bridges', Inorganic Chemistry, vol. 48, no. 8, pp. 3562-3572. https://doi.org/10.1021/ic801953z

Organometallic complexes for nonlinear optics. 43. Quadratic optical nonlinearities of dipolar alkynylruthenium complexes with phenyleneethynylene/ phenylenevinylene bridges. / Rigamonti, Luca; Babgi, Bandar; Cifuentes, Marie P. et al.
In: Inorganic Chemistry, Vol. 48, No. 8, 20.04.2009, p. 3562-3572.

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

TY - JOUR

T1 - Organometallic complexes for nonlinear optics. 43. Quadratic optical nonlinearities of dipolar alkynylruthenium complexes with phenyleneethynylene/ phenylenevinylene bridges

AU - Rigamonti, Luca

AU - Babgi, Bandar

AU - Cifuentes, Marie P.

AU - Roberts, Rachel L.

AU - Petrie, Simon

AU - Stranger, Robert

AU - Righetto, Stefania

AU - Teshome, Ayele

AU - Asselberghs, Inge

AU - Clays, Koen

AU - Humphrey, Mark G.

PY - 2009/4/20

Y1 - 2009/4/20

N2 - The syntheses of trans-[Ru(4,4′-C≡CC6H 4C≡CC6H4NO2)Cl(dppe) 2] (19) and the systematically varied complexes trans-[Ru(4,4′, 4′′-C≡CC6H4X2C 6H4Y2C6H4NO 2)Cl(L2)2] [L2 = dppe, X2 = C≡C, Y2 = (E)-CH=CH (12), C≡C (18); L2 = dppe, X2 = (E)-CH)CH, Y2 = C≡C (14), (E)-CH)CH (16); L2 = dppm, X2 = C≡C, Y2 = (E)-CH)CH (13); L2 = dppm, X2 = (E)-CH=CH, Y2 = C≡C (15), (E)-CH)CH (17)] are reported, the latter being donorbridge- acceptor complexes varying in bridge composition by replacement of yne with E-ene linkages, together with their cyclic voltammetric data, linear optical, and quadratic nonlinear optical response data. RuII/III oxidation potentials increase on replacing yne linkage by E-ene linkage at the phenylene adjacent to the metal center, and on replacing dppe by dppm co-ligands. The low-energy optical absorption maxima occur in the region 20400-23300 cm -1 and are metal-to-ligand charge-transfer (MLCT) in origin; these bands undergo a blue-shift upon π-bridge lengthening by addition of phenyleneethynylene units, and on replacing E-ene linkages by yne linkages. Time-dependent density functional theory calculations on model complexes have suggested assignments for the low-energy bands. The optical spectra of selected oxidized species contain low-energy ligand-to-metal charge transfer (LMCT) bands centered in the region 9760-11800 cm-1. Quadratic molecular nonlinearities from hyper-Rayleigh scattering (HRS) studies at 1064 nm reveal an increase in the two-level-corrected β0 value on π-bridge lengthening, a trend that is not seen with β values because of the blue-shift in λmax for this structural modification. Replacing yne linkages by E-ene linkage at the phenylene adjacent to the metal center or dppm co-ligand by dppe results in an increase in β and β0 values. In contrast, quadratic molecular nonlinearities by HRS at 1300 nm or electric field-induced secondharmonic generation (EFISH) studies at 1907 nm do not afford clear trends.

AB - The syntheses of trans-[Ru(4,4′-C≡CC6H 4C≡CC6H4NO2)Cl(dppe) 2] (19) and the systematically varied complexes trans-[Ru(4,4′, 4′′-C≡CC6H4X2C 6H4Y2C6H4NO 2)Cl(L2)2] [L2 = dppe, X2 = C≡C, Y2 = (E)-CH=CH (12), C≡C (18); L2 = dppe, X2 = (E)-CH)CH, Y2 = C≡C (14), (E)-CH)CH (16); L2 = dppm, X2 = C≡C, Y2 = (E)-CH)CH (13); L2 = dppm, X2 = (E)-CH=CH, Y2 = C≡C (15), (E)-CH)CH (17)] are reported, the latter being donorbridge- acceptor complexes varying in bridge composition by replacement of yne with E-ene linkages, together with their cyclic voltammetric data, linear optical, and quadratic nonlinear optical response data. RuII/III oxidation potentials increase on replacing yne linkage by E-ene linkage at the phenylene adjacent to the metal center, and on replacing dppe by dppm co-ligands. The low-energy optical absorption maxima occur in the region 20400-23300 cm -1 and are metal-to-ligand charge-transfer (MLCT) in origin; these bands undergo a blue-shift upon π-bridge lengthening by addition of phenyleneethynylene units, and on replacing E-ene linkages by yne linkages. Time-dependent density functional theory calculations on model complexes have suggested assignments for the low-energy bands. The optical spectra of selected oxidized species contain low-energy ligand-to-metal charge transfer (LMCT) bands centered in the region 9760-11800 cm-1. Quadratic molecular nonlinearities from hyper-Rayleigh scattering (HRS) studies at 1064 nm reveal an increase in the two-level-corrected β0 value on π-bridge lengthening, a trend that is not seen with β values because of the blue-shift in λmax for this structural modification. Replacing yne linkages by E-ene linkage at the phenylene adjacent to the metal center or dppm co-ligand by dppe results in an increase in β and β0 values. In contrast, quadratic molecular nonlinearities by HRS at 1300 nm or electric field-induced secondharmonic generation (EFISH) studies at 1907 nm do not afford clear trends.

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U2 - 10.1021/ic801953z

DO - 10.1021/ic801953z

M3 - Article

SN - 0020-1669

VL - 48

SP - 3562

EP - 3572

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -

Organometallic complexes for nonlinear optics. 43. Quadratic optical nonlinearities of dipolar alkynylruthenium complexes with phenyleneethynylene/ phenylenevinylene bridges

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