A cluster model of M I M II -MFU-4l MOFs was employed. In this model, we truncated all btdd 2-linkers to benzotriazolate (bta -) terminal ligands, producing the stoichiometry of the cluster M I M II 4Cl3(bta)6, where M I and M II are the metal atoms that can be independently varied. In the present study, we examined a set of atoms that includes M I = Cu I , Ag I , Au I , Ni I , Co I , and M II = Be II , Mg II , Zn II , Mn II , Cd II , Ca II , Sr II , Ba II . Other peripheral M I metal atoms such as Mn I , Cr I , Tl I , and alkali metals (K I , Rb I , Cs I ) were also tested with Zn II as the central atom. However, these combinations either resulted in excessively strong (Mn I , Cr I ) or weak (alkali metals, Tl I ) binding. In this study, we focused on the mono-substituted clusters (with one M I site) as previous work has demonstrated that sequential binding at various sites within the same cluster does not significantly affect the energetics of binding. Geometry optimization and vibrational analysis were performed using the B3LYP hybrid functional with Grimme's D3BJ dispersion correction to the DFT energy and Becke-Johnson damping. The small, but well-balanced double-zeta def2-SVP basis set was used for these calculations. Geometry optimization and thermochemistry calculations were performed using the ORCA 5.0.3 software. Frequency calculations were carried out using the harmonic approximation. A thermochemical analysis based on ideal gas statistical mechanics was performed. To correct the breakdown of the harmonic oscillator approximation for low frequencies, entropic contributions to the free energies were computed using the quasi-RRHO approach of Grimme, where frequencies below 100 cm -1 were treated as free rotors instead of harmonic oscillators. The C1 point group symmetry was used for all computations in ORCA. To obtain more accurate single point electronic energies, all optimized structures were re-evaluated using single point ωB97M-V/def2-TZVPPD calculations. ωB97M-V is a range separated hybrid meta-GGA functional with VV10 non-local dispersion, which showed one of the best performances in several large assessments. The binding enthalpies and Gibbs free energies were computed for the reactions M I M II 4Cl3(bta)6 + H2 = H2•••M I M II 4Cl3(bta)6 at the ωB97M-V/def2-TZVPPD//B3LYP-D3BJ/def2-SVP level. All open-shell states were computed within the unrestricted Kohn-Sham formalism. The spin state of Mn II ions was assumed to be a quintet (S = 5/2). Due to the weak ligand field, the triplet state (S = 1) of Co I was considered. Although the Co I singlet state can be assumed as a potential spin configuration in our case, our analysis revealed that the energy of the singlet state in Co I Zn II 4Cl3(bta)6 is 146 kJ/mol higher than that of the triplet state (B3LYP-D3BJ/def2-SVP level). This significant energy difference suggests the formation of the singlet state is highly unlikely.