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

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• 作者：Floriane Malvolti ; Cedric Rouxel ; Guillaume Grelaud ; Loic Toupet ; Thierry Roisnel ; Adam Barlow ; Xinwei Yang ; Genmiao Wang ; Fazira I. Abdul Razak ; Robert Stranger ; Marie P. Cifuentes ; Mark G. Humphrey ; Olivier Mongin ; Mireille Blanchard-Desce ; Christine O. Paul-Roth and Fré ; dé ; ric Paul
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：August 2016
• 年：2016
• 卷：2016
• 期：24
• 页码：3868-3882
• 全文大小：2466K
• ISSN：1099-0682c

文摘

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.