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Iron and Ruthenium Alkynyl Complexes with 2-Fluorenyl Groups: Some Linear and Nonlinear Optical Absorption Properties

Abstract : Four new mononuclear alkynyl complexes each featuring a terminal 2-fluorenyl group, namely Fe(η5-C5Me5)(CO)2[C≡C(2-C21H25)] (2), Ru(κ2-dppe)2Cl[C≡C(2-C21H25)] (3), Ru(κ2-dppe)2[C≡C(4-C6H4NO2)][C≡C(2-C21H25)] (4), and [Fe(η5-C5Me5)(κ2-dppe)_C≡C(C5H4N)-CH2(2-C13H9)_][PF6] (5[PF6]), have been synthesized and characterized, and their redox, absorption, and emission properties have been studied. For the two ruthenium derivatives 3 and 4, these studies are complemented by spectroelectrochemical investigations, Z-scan measurements, and DFT calculations. Fluorimetric studies reveal that these compounds are poorly or not luminescent, and, when luminescent, that the detected weak luminescence most likely originates from a higher lying ligand-centred (LC) excited state presumably located on fluorene. Finally, the third-order nonlinear optical (NLO) properties of 3 and 4 are reported. It is shown that the bis-alkynyl complex 4 is significantly more active than 3 and that both compounds exhibit two-photon absorption (TPA) around 860–1050 nm, with TPA cross-sections above 350 GM. In addition, it is shown that both species should give rise to a marked switching of their cubic NLO properties in this spectral range upon oxidation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01367214
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Submitted on : Thursday, September 15, 2016 - 5:17:07 PM
Last modification on : Wednesday, October 14, 2020 - 4:07:48 AM

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F. Malvolti, C. Rouxel, G. Grelaud, Loic Toupet, T. Roisnel, et al.. Iron and Ruthenium Alkynyl Complexes with 2-Fluorenyl Groups: Some Linear and Nonlinear Optical Absorption Properties. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2016, 2016 (24), pp.3868--3882. ⟨10.1002/ejic.201600598⟩. ⟨hal-01367214⟩

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