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Title: Mono(¿5-cyclopentadienyl)metal(II) Complexes with Thienyl Acetylide Chromophores: Synthesis, Electrochemical Studies, and First Hyperpolarizabilities
Authors: Silva, Tiago J.L.
Mendes, Paulo J.
Santos, Ana M.
Garcia, M. Helena
Robalo, M. Paula
Ramalho, J. P. Prates
Carvalho, Alfredo Jorge Palace
Büchert, Marina
Wittenburg, Christian
Heck, Jürgen
Keywords: Nonlinear optical properties
Quadratic hyperpolarizability
transition metal complexes
Hyper-Rayleigh scattering
Ruthenium sigma-acetylides
Organometallic complexes
Issue Date: 2014
Citation: Silva, Tiago J.L.; Mendes, Paulo J.; Santos, Ana M.; Garcia, M. Helena; Robalo, M. Paula; Ramalho, J. P. Prates; Carvalho, Alfredo Jorge Palace; Büchert, Marina; Wittenburg, Christian; Heck, Jürgen. Mono(¿5-cyclopentadienyl)metal(II) Complexes with Thienyl Acetylide Chromophores: Synthesis, Electrochemical Studies, and First Hyperpolarizabilities, Organometallics, 33, 18, 4655-4671, 2014.
Abstract: A series of mono(η5-cyclopentadienyl)metal- (II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(η5-C5H5)(L)(CC{C4H2S}nNO2)] (M = Fe, L = κ2-DPPE, n = 1, 2; M = Ru, L= κ2-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV−Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (β) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the secondorder nonlinear optical properties in these complexes. In this series, the complexity of the push−pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push−pull systems.
Other Identifiers: 0276-7333
Type: article
Appears in Collections:CQE - Publicações - Artigos em Revistas Internacionais Com Arbitragem Científica

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