The direct redox reaction between tetracyanoethylene (TCNE) and meso-tetraphenylporphyrinatoiron(II), [FeII(TPP)], formed the electron transfer salt (ETS) [FeIII(TPP)][TCNE], which has been structurally, spectroscopically, and magnetically characterized. It has an extended one-dimensional linear chain with coordination polymer motif comprised of [FeIII(TPP)]+ and bridging μ-[TCNE].- with Fe-NTCNE distance 1.889(2) Å. This coordination geometry is consistent with a low-spin iron(III) ion, i.e., one electron transfer from FeII to TCNE produces S = 1/2 [FeIII(TPP)]+ having a (dxy)2(dyz,dzx)3 configuration and S = 1/2 [TCNE].-. 57Fe Mössbauer data, δ = 0.28 mm s-1 and ΔE = 2.19 mm s-1 at 77 K, also support the low-spin state. The room temperature magnetic moment of the ETS, 1.20 μB, arises from two S = 1/2 systems having antiferromagnetic coupling, -190 cm-1 (H = -2Σ J ijSiSj).
|Number of pages||8|
|Journal||Journal of the Chemical Society, Dalton Transactions|
|Publication status||Published - 2001 Dec 1|
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