Use of the TCNQF4 2- Dianion in the Spontaneous Redox Formation of [FeIII (L- )2 ][TCNQF4 ⋅- ]

Abstract

The reaction of [Fe^II (L^. )₂ ](BF₄ )₂ with Li₂ TCNQF₄ results in the formation of [Fe^III (L^- )₂ ][TCNQF₄ ^{. -} ] (1) where L^. is the radical ligand, 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N-oxide and TCNQF₄ is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. This has been characterised by X-ray diffraction, Raman and Fourier transform infrared (FTIR) spectroscopy, variable-temperature magnetic susceptibility, Mössbauer spectroscopy and electrochemistry. X-ray diffraction studies, magnetic susceptibility measurements and Raman and FTIR spectroscopy suggest the presence of low-spin Fe^III ions, the anionic form (L^- ) of the ligand and the anionic radical form of TCNQF₄ ; viz. TCNQF₄ ^{. -} . Li₂ TCNQF₄ reduces the [Fe^II (L^. )₂ ]²⁺ dication, which undergoes a reductively induced oxidation to form the [Fe^III (L^- )₂ ]⁺ monocation resulting in the formation of [Fe^III (L^- )₂ ][TCNQF₄ ^{. -} ] (1), the electrochemistry of which revealed four well-separated, diffusion-controlled, one-electron, reversible processes. Mössbauer spectroscopy and electrochemical measurements suggest the presence of a minor second species, likely to be [Fe^II (L^. )₂ ][TCNQF₄ ^2- ].

Keywords: charge transfer; electrochemistry; iron; magnetic properties; radicals.