Utilize este identificador para referenciar este registo: http://hdl.handle.net/10400.21/4948
Título: Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities
Autor: Silva, Tiago J. L.
Mendes, Paulo J.
Santos, Ana Margarida
Garcia, Maria Helena
Robalo, Maria Paula Alves
Ramalho, J. P. Prates
Carvalho, A. J. Palace
Buechert, Marina
Wittenburg, Christian
Heck, Juergen
Palavras-chave: Nonlinear optical properties
Molecular quadratic hyperpolarizabilities
Transition-meta-complexes
Hyper-rayleigh scattering
Ray crystal-structures
Ruthenium sigma-acetylides
Organometallic complexes
X-ray
Cubic hyperpolarizabilities
Structural characterization
Data: Set-2014
Editora: Amer Chemical Society
Citação: SILVA, Tiago J. L.; [et al] – Mono(Eta(5)-Cyclopentadienyl)Metal(II) Complexes with Thienyl Acetylide Chromophores: Synthesis, electrochemical studies, and first hyperpolarizabilities. Organometallics. ISSN: 0276-7333. Vol. 33, nr, 18 (2014), pp. 4655-4671
Resumo: A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-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 (beta) 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 second-order 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.
Peer review: yes
URI: http://hdl.handle.net/10400.21/4948
DOI: 10.1021/om4001204
ISSN: 0276-7333
1520-6041
Aparece nas colecções:ISEL - Eng. Quim. Biol. - Artigos

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