The chiral triplesalen ligand H₆chand^RR has been used to synthesize the chiral heptanuclear complexes [{(chand^RR)Mn^III₃}₂{Fe^II(CN)₆}](ClO₄)₂ (^RR[Mn^III₆Fe^II](ClO₄)₂) and [{(chand^RR)Fe^III₃}₂{Fe^II(CN)₆}](ClO₄)₂ (^RR[Fe^III₆Fe^II](ClO₄)₂), which have been characterized by single-crystal X-ray diffraction, mass spectrometry, elemental analysis, FT-IR, Mössbauer, and UV-vis spectroscopies, electrochemistry, as well as DC and AC magnetic susceptibility measurements. The half-wave potential of the Fe^III/Fe^II couple in ^RR[Mn^III₆Fe^II]²⁺ and ^RR[Fe^III₆Fe^II]²⁺ is E_1/2 = +0.21 and +0.75 V vs. Fc⁺/Fc, respectively, which (i) corresponds to a strong stabilization of the reduced Fe^II species compared to the redox couple of free [Fe^II/III(CN)₆]^4−/3− and (ii) indicates a significant difference of the electronic coupling with the {(chand^RR)M^t}³⁺ units (M^t = Mn^III, Fe^III). Analysis of the DC magnetic data (μ_effvs. T, VTVH) of both complexes by a full-matrix diagonalization of the spin-Hamiltonian including isotropic exchange, zero-field splitting with full consideration of the relative orientation of the D tensors and Zeeman interactions reveals ferromagnetic interactions of J_Mn–Mn = +0.17 ± 0.02 cm⁻¹ with D_Mn = −3.4 ± 0.3 cm⁻¹ for ^RR[Mn^III₆Fe^II]²⁺ and J_Fe–Fe = +0.235 ± 0.005 cm⁻¹ with D_Fe = 0 for ^RR[Fe^III₆Fe^II]²⁺. The comparison of the molecular structures of ^RR[Mn^III₆Fe^II]²⁺ and ^RR[Fe^III₆Fe^II]²⁺ with those of the heptanuclear complexes [M^t₆M^c]ⁿ⁺ using the achiral triplesalen ligand (talen^t-Bu₂)⁶⁻ reveals significant differences in the ligand folding, smaller C–C bond distances in the central phloroglucinol ring and larger HOMA values. This indicates more aromatic character and less heteroradialene contribution in ^RR[Mn^III₆Fe^II]²⁺ and ^RR[Fe^III₆Fe^II]²⁺, which explains the switching from antiferromagnetic coupling in [M^t₆M^c]ⁿ⁺ to ferromagnetic coupling in ^RR[M^t₆M^c]ⁿ⁺ by a stronger contribution of the spin-polarization mechanism. This establishes a magnetostructural correlation between the structural parameters describing the aromaticity of the central phloroglucinol unit and the observed exchange couplings J_Mn–Mn.