The inverted triplesalen ligand H6feldMe has been synthesized from 2,4,6-triformyl-phloroglucinol and a ketimine salen half-unit in a convergent synthesis. NMR, IR, and UV-vis spectroscopy reveal that this ligand is not in the O-protonated tautomer but in the N-protonated tautomer with substantial heteroradialene contribution. This ligand and the conventional triplesalen ligand H6talent-Bu2 have been used to synthesize the trinuclear Fe~(Ⅲ)_3 complexes [(feldMe)(FeCl)3] and [(talent-Bu2)(FeCl)3], respectively. The molecular structures of these complexes were obtained by single-crystal X-ray diffraction. Two trinuclear Fe~(Ⅲ)_3 complexes of [(feldMe)(FeCl)3] dimerize via two Fe-phenolate bonds, whereas due to steric hindrance no dimerization is observed for [(talent-Bu2)(FeCl)3]. The structural data also reveal some heteroradialene contribution in the trinuclear complexes. Whereas UV-vis and Mβbauer spectroscopy are not suitable to distinguish between the two complexes, FT-IR spectra show characteristic features due to the different substitution patterns of the conventional and the inverted triplesalen ligands. Another handle is provided by electrochemistry. Whereas both complexes exhibit an irreversible oxidation wave (0.94 V vs. Fc+/Fc for [(feldMe)(FeCl)3] and 0.84 V vs. Fc+/Fc for [(talent-Bu2)(FeCl)3]), which is assigned to the oxidation of the central backbone, higher potential oxidations are reversible for [(talent-Bu2)(FeCl)3]) but irreversible for [(feldMe)(FeCl)3]. This is attributed to the reversible oxidation of the terminal phenolates in the di-tert-butyl substituted [(talent-Bu2)(FeCl)3] in contrast to the mono-methyl-substituted phenolates in [(feldMe)(FeCl)3]. The magnetic properties of [(talent-Bu2)(FeCl)3] reveal a very small ferromagnetic coupling with significant zero-field splitting of the Fe~(Ⅲ)_3 S = 5/2 ions. In contrast, the dimerization of two trinuclear complexes in [(feldMe)(FeCl)3] results in antiferromagnetic interactions between the two phenolate-bridged Fe~(Ⅲ)_3 ions, which mask the intra-trinuclear interactions transmitted by the central phloroglucinol backbone. The inverted triplesalen ligand H6feldMe has been synthesized from 2,4,6-triformyl-phloroglucinol and a ketimine salen half-unit in a convergent synthesis. NMR, IR, and UV-vis spectroscopy reveal that this ligand is not in the O-protonated tautomer but in the N-protonated tautomer with substantial heteroradialene contribution. This ligand and the conventional triplesalen ligand H6talent-Bu2 have been used to synthesize the trinuclear Fe ~ (Ⅲ) _3 complexes [(feldMe) (FeCl) 3] and [(talent -Bu2) (FeCl) 3], respectively. The molecular structures of these complexes were obtained by single-crystal X- ray diffraction. Two trinuclear Fe ~ (Ⅲ) _3 complexes of [(feldMe) (FeCl) 3] dimerize via two Fe-phenolate bonds, while due to steric hindrance no dimerization was observed for [(talent-Bu2) (FeCl) 3]. The structural data also reveal some heteroradialene contributions in the trinuclear complexes. Whereas UV-vis and Mβbauer spectroscopy are not suitable to distinguish between the two complexes, FT-IR sp ectra show characteristic features due to the different substitution patterns of the conventional and the inverted triplesalen ligands. Another handle is provided by electrochemistry. Whereas both complexes exhibit an irreversible oxidation wave (0.94 V vs. Fc + / Fc for [(feldMe) (FeCl) (Talent-Bu2) (FeCl) 3]) which is assigned to the oxidation of the central backbone, higher potential oxidations are reversible for [(talent-Bu2) (FeCl) 3] and 0.84 V vs. Fc + / Fc for [ 3]) but irreversible for [(feldMe) (FeCl) 3]. This is attributed to the reversible oxidation of the terminal phenolates in the di-tert-butyl substituted [(talent-Bu2) (FeCl) 3] in contrast to the mono-methyl-substituted phenolates in [(feldMe) (FeCl) 3]. The magnetic properties of [(talent-Bu2) (FeCl) 3] reveal a very small ferromagnetic coupling with significant zero-field splitting of the Fe ~ ) _3 S = 5/2 ions. In contrast, the dimerization of two trinuclear complexes in [(feldMe) (FeCl) 3] results in antiferromagnetic interactions betwe en the two phenolate-bridged Fe ~ (Ⅲ) _3 ions, which mask the intra-trinuclear interactions transmitted by the central phloroglucinol backbone.