Benzo[c]thiophene Chromophores Linked to Cationic Fe and Ru Derivatives for NLO Materials: Synthesis Characterization and Quadratic Hyperpolarizabilities. Issue 20 (31st May 2013)

• Record Type: Journal Article
• 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
• Is Part Of: European journal of inorganic chemistry. Issue 20(2013)
• Page Start: 3506
• Page End: 3517
• Publication Date: 2013-05-31
• Subjects: Ruthenium -- Iron -- Sulfur ­heterocycles -- Nonlinear optics -- Hyper­polarizabilities; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201300048
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: η 5 ‐Monocyclopentadienyliron(II)/ruthenium(II) complexes of the general formula [M(η 5 ‐C5 H5 )(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. Abstract : η 5 ‐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.