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Multistate Redox-Active Metalated Triarylamines

Abstract : trans-[(η5-C5H5)Fe(η5-C5H4-η1-C≡C)Ru(C≡C-4-C6H4NPh2)(dppe)2] [4; dppe = 1,2-bis(diphenylphosphanyl)ethane] and trans,trans,trans-[₍η5-C5H5)Fe(η5-C5H4-η1-C≡C)Ru(dppe)2(C≡C-4-C6H4)₃N] (7) have been synthesized from trans-[Ru(C≡C-4-C6H4NPh2)Cl(dppe)2] (3) and trans,trans,trans-[₍dppe)2ClRu(C≡C-4-C6H4)₃N] (6), respectively, and the identities of trans-[Ru(C=CH-4-C6H4NPh2)Cl(dppe)2][PF6] (2, precursor to 3), 3, and 4 have been confirmed crystallographically. Chemical oxidation of 4 and 7 afforded the isolable mixed-valence species 4[PF6] and 7[PF6]3. The CV of 4 reveals sequential loss of three electrons in fully reversible oxidation steps, whereas the CV of 7 shows five reversible redox waves; in contrast, oxidation of the precursor amines HC≡C-4-C6H4NPh2 and (HC≡C-4-C6H4)3N are irreversible processes. All oxidation processes afford reversible changes in the linear optical properties. Complementary time-dependent density functional theory (TD-DFT) studies suggest that the initial oxidation process for 4 and 7 is iron-centered and is followed by one (for 4) or three (for 7) ruthenium-centered oxidations. The final reversible oxidation is assigned by TD-DFT as delocalized along the metalla-ethynylarylamine moiety. The intense optical changes consequent on reversible oxidation, together with their charge-transfer character, suggest that 4 and 7 have potential as nonlinear as well as linear optical multistate switches.
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Submitted on : Thursday, February 16, 2017 - 9:35:59 AM
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Guillaume Grelaud, Marie P. Cifuentes, Torsten Schwich, Gilles Argouarch, Simon Petrie, et al.. Multistate Redox-Active Metalated Triarylamines. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2012, 2012, pp.65-75. ⟨10.1002/ejic.201100747⟩. ⟨hal-01468974⟩



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