Benzene–Ni<sub>10</sub>S<sub>20</sub> Interaction.\nHost–Guest Features and Nuclear Magnetic Resonance Patterns\ntoward Prototypical Metal-Based Active Cavities

The formation of active pores for the formation of metal–organic\nframeworks is relevant in materials science, encouraging the design\nof metal-based host structures. Here, we explore the features leading\nto the arene incorporation into Ni<sub>10</sub>S<sub>20</sub> frameworks\nvia computational methods. The resulting host–guest aggregation\ninvolves favorable interaction energies in the range of ∼ 30\nkcal/mol, given by the similar contribution from electrostatic, orbital,\nand London stabilizing interactions and their interplay to steric\nrepulsions, which rules the resulting orientation of the arene moiety\ninto the Ni<sub>10</sub>S<sub>20</sub> backbone. In addition, palladium\nand platinum counterparts were evaluated, suggesting related capabilities\nfor group X metal-based cavities. Such properties can be further tuned\nby variation of the M<sub>10</sub> backbone and side functional groups,\nleading to suitable metallic cavities as prototypical pores to be\nincluded in metal–organic frameworks (MOFs) for the incorporation\nof volatile organic compounds (VOCs) units. In addition, smaller and\nlarger cavity sizes given by related M<sub>8</sub>S<sub>16</sub> and\nM<sub>12</sub>S<sub>24</sub> hosts decrease largely the interaction\ntoward benzene, quenching effective sequestering capabilities. Thus,\nthe size of ten-metal cavities is proper for further fixation of benzene\ninto metal–organic active sites. Calculated nuclear magnetic\npatterns suggest a deshielding shift for incorporated arene units,\nwhich are useful features to probe diffusion and orientation of the\nincoming VOCs. Thus, exploration of group X tiara-like structures\nmay stimulate further applications toward sensing and treatment of\ndifferent VOC species for designing versatile MOFs.