| Summary: | The dichotomy between metal–organic frameworks (MOFs) and metal–organic cages (MOCs) opens up the research spectrum of two fields which, despite having similarities, both have their advantages and disadvantages. Due to the fact that they have cavities inside, they also have applicability in the porosity sector. Bloch and coworkers within this evolution from MOFs to MOCs manage to describe a MOC with a structure of Cu<sub>2</sub> paddlewheel Cu<sub>4</sub>L<sub>4</sub> (L = bis(pyrazolyl)methane) with high precision thanks to crystallographic analyses of X-ray diffraction and also SEM-EDX. Then, also at the same level of concreteness, they were able to find the self-assembly of Pd(II)Cl<sub>2</sub> moieties on the available nitrogen donor atoms leading to a [Cu<sub>4</sub>(L(PdCl<sub>2</sub>))<sub>4</sub>] structure. Here, calculations of the DFT density functional allow us to reach an unusual precision given the magnitude and structural complexity, explaining how a pyrazole ring of each bis(pyprazolyl)methane ligand must rotate from an <i>anti</i> to a <i>syn</i> conformation, and a truncation of the MOC structure allows us to elucidate, in the absence of the MOC constraint and its packing in the crystal, that the rotation is almost barrierless, as well as also explain the relative stability of the different conformations, with the <i>anti</i> being the most stable conformation. Characterization calculations with Mayer bond orders (MBO) and noncovalent interaction (NCI) plots discern what is important in the interaction of this type of cage with PdCl<sub>2</sub> moieties, also CuCl<sub>2</sub> by analogy, as well as simple molecules of water, since the complex is stable in this solvent. However, the L ligand is proved to not have the ability to stabilize an H<sub>2</sub>O molecule.
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