Metal−ligand coordination interactions are usually much stronger than weak intermolecular interactions. Nevertheless, here, we show experimental evidence and theoretical confirmation of a very rare example where metal−ligand bonds dissociate in an irreversible way, helped by a large number of weak intermolecular interactions that surpass the energy of the metal−ligand bond. Thus, we describe the design and synthesis of trinuclear Mn 2 Fe complex {[Mn(L)-(H 2 O)] 2 Fe(CN) 6 }, 2− starting from a mononuclear Mn(III)-Schiff base complex: [Mn(L)(H 2 O)Cl] (1) and [Fe(CN) 6 ] 4− anions. This reaction implies the dissociation of Mn(III)-Cl coordination bonds and the formation of Mn(III)-NC bonds with the help of several intermolecular interactions. Here, we present the synthesis, crystal structure, and magnetic characterization of the monomeric Mn))bis(methaneylylidene))bis(4-methoxyphenol)). Complex 1 is a monomer where the Schiff base ligand (L) is coordinated to the four equatorial positions of the Mn(III) center with a H 2 O molecule and a Cl − ion at the axial sites and the monomeric units are assembled by π−π and hydrogen-bonding interactions to build supramolecular dimers. The combination of [Fe(CN) 6 ] 4− with complex 1 leads to the formation of linear Mn-NC-Fe-CN-Mn trimers where two trans cyano groups of the [Fe(CN) 6 ] 4− anion replace the labile chloride from the coordination sphere of two [Mn(L)(H 2 O)Cl] complexes, giving rise to the linear anionic {[Mn(L)(H 2 O)] 2 Fe(CN) 6 } 2− trimer. This Mn 2 Fe trimer crystallizes with an oxonium cation and a mononuclear [Mn(L)(H 2 O) 2 ] + cation, closely related to the precursor neutral complex [Mn(L)(H 2 O)Cl]. In compound 2, the Mn 2 Fe trimers are assembled by several hydrogen-bonding and π−π interactions to frame an extended structure similar to that of complex 1. Density functional theoretical (DFT) calculations at the PBE1PBE-D3/def2-TZVP level show that the bond dissociation energy (−29.3 kcal/mol) for the Mn(III)-Cl bond is smaller than the summation of all the weak intermolecular interactions (−30.1 kcal/mol). Variable-temperature magnetic studies imply the existence of weak intermolecular antiferromagnetic couplings in both compounds, which can be can cancelled with a critical field of ca. 2.0 and 2.5 T at 2 K for compounds 1 and 2, respectively. The magnetic properties of compound 1 have been fit with a simple S = 2 monomer with g = 1.959, a weak zero-field splitting (|D| = 1.23 cm −1 ), and a very weak intermolecular interaction (zJ = −0.03 cm −1 ). For compound 2, we have used a model with an S = 2 monomer with ZFS plus an S = 2 antiferromagnetically coupled dimer with g = 2.009, |D| = 1.21 cm −1 , and J = −0.42 cm −1 . The metamagnetic behavior of both compounds is attributed to the weak intermolecular π−π and hydrogen-bonding interactions.