The reaction of H2salpn (H2salpn = N,N′-bis(salicylidene)-1,3-propanediamine) with Fe(ClO4)3 in a ratio of 1 : 1 and 3 : 2, leads to dark red crystals of the solvatomorphs [(salpn)Fe(μ2-salpn)Fe(salpn)]·0.5MeOH (1) and [(salpn)Fe(μ2-salpn)Fe(salpn)]·MeOH (2), respectively. X-Ray crystallographic studies reveal a slightly distorted octahedral geometry and meridional configuration of the N and O donor atoms with one of the salpn ligands acting as a bridge between the two FeIII atoms to create a dimer. The Fe–N/O bond distances for both dimers indicate that the Fe centres are high spin. Supramolecular dimeric pairs are formed in both structures from C–H···π and/or C–H···O interactions. However, the degree of solvation significantly impacts the arrangements of these dimeric pairs with tightly packed 1D chains in 2 and more loosely packed chains in 1. In addition, electrochemical studies reveal weak communication between the two Fe atoms despite the large distance between them and the lack of conjugation across the bridge.