Organometallic complexes for nonlinear optics. 41: Syntheses and quadratic NLO properties of 4-{4-(4-nitrophenyl)diazophenyl}ethynylphenylethynyl complexes

Fondum, Timothy N.; Green, Katy A.; Randles, Michael D.; Cifuentes, Marie P.; Willis, Anthony C.; Teshome, Ayele; Asselberghs, Inge; Clays, Koen; Humphrey, Mark G.

doi:10.1016/j.jorganchem.2007.11.004

Cited by 12 publications

(4 citation statements)

References 30 publications

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“…Figure contains an ORTEP plot showing the molecular geometry, together with selected bond lengths and angles. Bond lengths and angles are similar to those of the structurally characterized analogues trans -[Ru(CC-4-C 6 H 4 CCC 6 H 4 -4-X)Cl(dppm) 2 ] (X = H, NNC 6 H 4 -4-NO 2 ), the only notable exception being Cl1−Ru1−Cl 170.33(9)° ( 19 ), cf. 175.9(2)° (X = H), 175.1(17)° (X = NNC 6 H 4 -4-NO 2 ), a distortion in 19 likely to derive from the need to minimize unfavorable steric interactions between the C4-ethoxy group and the P-phenyl rings.…”

Section: Resultsmentioning

confidence: 69%

“…The new alkynyl complexes 19 − 24 were prepared using established methodologies (Schemes and ) ,,− and characterized by a combination of IR, 1 H, 13 C, and 31 P NMR spectroscopies and ESI mass spectrometry. The IR spectra contain characteristic ν(CC) bands at 2063−2074 cm −1 for the metal-bound alkynyl group, with the higher values corresponding to complexes with the longer π-bridges ( 22 − 24 ).…”

Section: Resultsmentioning

confidence: 99%

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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

et al. 2009

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The syntheses of trans-[Ru{4,4'-C[triple bond]CC(6)H(2)[2,5-(OEt)(2)]C[triple bond]CC(6)H(4)NO(2)}Cl(dppm)(2)] (19), trans-[Ru{4,4',4''-C[triple bond]CC(6)H(4)C[triple bond]CC(6)H(2)[2,5-(OEt)(2)]C[triple bond]CC(6)H(4)NO(2)}Cl(dppm)(2)] (20), trans-[Ru{4,4',4'',4'''-C[triple bond]CC(6)H(4)C[triple bond]CC(6)H(2)[2,5-(OEt)(2)]C[triple bond]CC(6)H(2)[2,5-(OEt)(2)]C[triple bond]CC(6)H(4)NO(2)}Cl(dppe)(2)] (21), trans-[Ru{4,4',4'',4'''-C[triple bond]CC(6)H(4)C[triple bond]CC(6)H(2)[2,5-(OEt)(2)]C[triple bond]CC(6)H(2)[2,5-(OEt)(2)]C[triple bond]CC(6)H(4)NO(2)}Cl(dppm)(2)] (22), trans-[Ru{4,4',4'',4'''-C[triple bond]CC(6)H(4)C[triple bond]CC(6)H(4)C[triple bond]CC(6)H(2)[2,5-(OEt)(2)]C[triple bond]CC(6)H(4)NO(2)}Cl(dppm)(2)] (23), and trans-[Ru{4,4',4'',4''',4''''-C[triple bond]CC(6)H(4)C[triple bond]CC(6)H(4)C[triple bond]CC(6)H(2)[2,5-(OEt)(2)]C[triple bond]CC(6)H(2)[2,5-(OEt)(2)]C[triple bond]CC(6)H(4)NO(2)}Cl(dppm)(2)] (24) are reported, together with those of precursor alkynes, complexes with the donor-pi-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 pi-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 pi-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 beta(1064) and two-photon absorption cross-section reach maximal values at this same pi-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.

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Section: Resultsmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

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

et al. 2009

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“…The synthetic methodology employed for the preparation of the new alkynyl complexes (Scheme ) has been successfully employed for the synthesis of related (chloro)bis(diphosphine)ruthenium complexes by several groups. ,,,− The new complexes 12 − 19 were characterized by IR, 1 H, 13 C, and 31 P NMR spectroscopy and ESI mass spectrometry. IR spectra contain characteristic ν(C≡C) bands at 2056−2067 cm −1 for the metal-bound alkynyl group, while the 31 P NMR spectra contain one singlet resonance each at 49.7−50.0 ppm (dppe-containing complexes) or −5.4 to −5.9 ppm (dppm-containing complexes), consistent with trans -disposed diphosphine ligands.…”

Section: Resultsmentioning

confidence: 99%

Organometallic Complexes for Nonlinear Optics. 43. Quadratic Optical Nonlinearities of Dipolar Alkynylruthenium Complexes with Phenyleneethynylene/Phenylenevinylene Bridges

et al. 2009

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The syntheses of trans-[Ru(4,4'-C[triple bond]CC(6)H(4)C[triple bond]CC(6)H(4)NO(2))Cl(dppe)(2)] (19) and the systematically varied complexes trans-[Ru(4,4',4''-C[triple bond]CC(6)H(4)X(2)C(6)H(4)Y(2)C(6)H(4)NO(2))Cl(L(2))(2)] [L(2) = dppe, X(2) = C[triple bond]C, Y(2) = (E)-CH=CH (12), C[triple bond]C (18); L(2) = dppe, X(2) = (E)-CH=CH, Y(2) = C[triple bond]C (14), (E)-CH=CH (16); L(2) = dppm, X(2) = C[triple bond]C, Y(2) = (E)-CH=CH (13); L(2) = dppm, X(2) = (E)-CH=CH, Y(2) = C[triple bond]C (15), (E)-CH=CH (17)] are reported, the latter being donor-bridge-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 20,400-23,300 cm(-1) and are metal-to-ligand charge-transfer (MLCT) in origin; these bands undergo a blue-shift upon pi-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 9760-11,800 cm(-1). Quadratic molecular nonlinearities from hyper-Rayleigh scattering (HRS) studies at 1064 nm reveal an increase in the two-level-corrected beta(0) value on pi-bridge lengthening, a trend that is not seen with beta values because of the blue-shift in lambda(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 beta and beta(0) values. In contrast, quadratic molecular nonlinearities by HRS at 1300 nm or electric field-induced second-harmonic generation (EFISH) studies at 1907 nm do not afford clear trends.

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“…Extinction coefficients are similar for Ru1 – Ru3 , and slightly lower for Ru4 (Table , Figure S9); this difference in the absorption band intensity is consistent with observations with the precursor alkynes but, in contrast to the alkynes, no clear additional band is apparent at higher energy (although the broad absorption profile makes such analysis difficult). Comparison of the λ max values to that of trans ‐[Ru(C≡C‐1‐C 6 H 4 ‐4‐C≡C‐1‐C 6 H 4 ‐4‐N=N‐1‐C 6 H 4 ‐4‐NO 2 )Cl(dppm) 2 ] ( Ru5 , Table ) confirms the red‐shift in proceeding from complexes with a distal diazene to complexes with a proximal electron‐withdrawing diazene group.…”

Section: Resultsmentioning

confidence: 99%

Syntheses and Optical Properties of Azo‐Functionalized Ruthenium Alkynyl Complexes

et al. 2016

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The syntheses of trans‐[Ru(C≡C‐1‐C6H4‐4‐N=N‐1‐C6H4‐4‐C≡C‐1‐C6H4‐4‐NO2)Cl(L2)2] (L2=dppm (Ru1), dppe) (Ru2)), trans‐[Ru(C≡C‐1‐C6H4‐4‐N=N‐1‐C6H4‐4‐(E)‐CH=CH‐1‐C6H4‐4‐NO2)Cl(dppe)2] (Ru3), and trans‐[Ru(C≡C‐1‐C6H4‐4‐(E)‐CH=CH‐1‐C6H2‐2,6‐Et2‐4‐N=N‐1‐C6H4‐4‐NO2)Cl(dppe)2] (Ru4) are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), linear optical and quadratic nonlinear optical (NLO) properties assayed by UV/Vis‐NIR spectroscopy and hyper‐Rayleigh scattering studies at 1064 nm, respectively, and their linear optical properties in the formally RuIII state examined by UV/Vis‐NIR spectroelectrochemistry. These data were compared to those of analogues with E‐ene and yne linkages in place of the azo groups. Computational studies using time‐dependent density functional theory were undertaken on model compounds (Ru2′–Ru4′) to rationalize the optical behaviour of the experimental complexes.

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Organometallic complexes for nonlinear optics. 41: Syntheses and quadratic NLO properties of 4-{4-(4-nitrophenyl)diazophenyl}ethynylphenylethynyl complexes

Cited by 12 publications

References 30 publications

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

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

Organometallic Complexes for Nonlinear Optics. 43. Quadratic Optical Nonlinearities of Dipolar Alkynylruthenium Complexes with Phenyleneethynylene/Phenylenevinylene Bridges

Syntheses and Optical Properties of Azo‐Functionalized Ruthenium Alkynyl Complexes

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