The first mechanism is studied in detail in two Hofmannlike MOFs, Fe(bpac)M(CN)4 and Fe(pz)M(CN)4 with M=Fe(II), Ni(II), and Mn(II). The large change in binding energy occurring concomitantly with the spin state change from low to intermediate spin is reported for CO, CO2, N2, and H2. These represent the ground state and the first accessible one in a thermally-induced sco transition. The feasibility of this novel process from a thermodynamic point of view is the most challenging aspect of the presented idea. Here, this is assessed by computing the adiabatic energy difference between the spin states involved in the transition. Motivated by our previous studies, we employ an efficient and yet accurate Hubbard U -density corrected scheme to compute both the adiabatic energy differences and the change in binding energy upon spin crossover. This method, already validated in the calculation of spin splittings of periodic compounds, consists in adopting the Hubbard Ucorrected density and a standard energy functional (without U ) so that a good description of the electronic density is achieved via DFT+U while the Hubbard term is removed in order to avoid the bias in the energy. We recall that in order to obtain the transition temperature, besides the adiabatic energy differences reported here, the vibrational enthalpy and entropy, and the electronic entropy are also required to compute the free energy change, ∆G=∆H-T∆S. Since the computed ∆EH-L reported above well approximate the total ∆H of the spin-state transition (the thermal contribution is usually very small), we consider that values of adiabatic energy differences ranging between 0.2 and 0.6 eV may be consistent with the proposed mechanism. This assumption is motivated by recent studies reporting these values of enthalpy change associated with near-room temperature spin crossover for several Fe(II)-based molecular and crystalline compounds. We stress here that while the calculation of T 1/2 is possible by evaluating all the terms that enter the free energy, this is beyond the scope of this work.