The complexes [Fe(HMC)(CDMA)]CFSO ([]OTf) and [Fe(HMTI)(CY)]CFSO ([-]OTf) have been prepared and thoroughly characterized (HMC = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; HMTI = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene; Y = Fc (ferrocenyl, []OTf), 4-(,-dimethyl)anilino (DMA, []OTf), or 4-(,-bis(4-methoxyphenyl)anilino (TPA, []OTf); OTf = CFSO)). Vibrational and electronic absorption spectroelectrochemical analyses following one-electron oxidation of the ethynyl substituent Y revealed evidence of strong coupling in the resultant mixed valent species for all HMTI-based complexes. However, the analogous mixed valent ion based on []OTf appeared to be more localized. Thus, the tetra-imino macrocycle HMTI has enabled significant valence delocalization along the -C-Fe-C- bridge. Electron paramagnetic resonance and Mössbauer spectroscopic studies of []OTf reveal that the π-acidity of HMTI lowers the energy of the Fe dπ orbitals compared to the purely σ-donating HMC. This observation provides a basis for the interpretation of the macrocycle-dependent valence (de)localization.
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