Benzo[c]thiophene Chromophores Linked to Cationic Fe and Ru Derivatives for NLO Materials: Synthesis Characterization and Quadratic Hyperpolarizabilities

η5‐Monocyclopentadienyliron(II)/ruthenium(II) complexes of the general formula [M(η5‐C5H5)(PP)(L1)][PF6] {M = Fe, PP = dppe; M = Ru, PP = dppe or 2PPh3; L1 = 5‐[3‐(thiophen‐2‐yl)benzo[c]thiophenyl]thiophene‐2‐carbonitrile} have been synthesized and studied to evaluate their molecular quadratic hyper...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2013-07, Vol.2013 (20), p.3506-3517
Main Authors: Silva, Tiago J. L., Mendes, Paulo J., Garcia, M. Helena, Robalo, M. Paula, Prates Ramalho, J. P., Palace Carvalho, A. J., Büchert, Marina, Wittenburg, Christian, Heck, Jürgen
Format: Article
Language:English
Subjects:
Cationic
Derivatives
Hyper­polarizabilities
Iron
Mathematical analysis
Nonlinear optics
Nonlinearity
Optical properties
Polypropylenes
Ruthenium
Scattering
Sulfur ­heterocycles
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Summary:η5‐Monocyclopentadienyliron(II)/ruthenium(II) complexes of the general formula [M(η5‐C5H5)(PP)(L1)][PF6] {M = Fe, PP = dppe; M = Ru, PP = dppe or 2PPh3; L1 = 5‐[3‐(thiophen‐2‐yl)benzo[c]thiophenyl]thiophene‐2‐carbonitrile} have been synthesized and studied to evaluate their molecular quadratic hyperpolarizabilities. The compounds were fully characterized by NMR, FTIR and UV/Vis spectroscopy and their electrochemical behaviour studied by cyclic voltammetry. Quadratic hyperpolarizabilities (β) were determined by hyper‐Rayleigh scattering measurements at a fundamental wavelength of 1500 nm. Density functional theory calculations were employed to rationalize the second‐order non‐linear optical properties of these complexes. η5‐Monocyclopentadienyliron(II)/ruthenium(II) complexes with 5‐[3‐(thiophen‐2‐yl)benzo[c]thiophenyl]thiophene‐2‐carbonitrile as ligand have been synthesized. Quadratic hyperpolarizabilities in the range of (105–164) × 10–30 esu were evaluated by hyper‐Rayleigh scattering at 1500 nm. DFT calculations were performed to explain their non‐linear optical properties.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201300048