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 - http://www.scopus.com/inward/record.url?scp=67651213432&partnerID=8YFLogxK
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 -