Benzene–Ni₁₀S₂₀ Interaction. Host–Guest Features and Nuclear Magnetic Resonance Patterns toward Prototypical Metal-Based Active Cavities

The formation of active pores for the formation of metal–organic frameworks is relevant in materials science, encouraging the design of metal-based host structures. Here, we explore the features leading to the arene incorporation into Ni10S20 frameworks via computational methods. The resulting host–guest aggregation involves favorable interaction energies in the range of ∼ 30 kcal/mol, given by the similar contribution from electrostatic, orbital, and London stabilizing interactions and their interplay to steric repulsions, which rules the resulting orientation of the arene moiety into the Ni10S20 backbone. In addition, palladium and platinum counterparts were evaluated, suggesting related capabilities for group X metal-based cavities. Such properties can be further tuned by variation of the M10 backbone and side functional groups, leading to suitable metallic cavities as prototypical pores to be included in metal–organic frameworks (MOFs) for the incorporation of volatile organic compounds (VOCs) units. In addition, smaller and larger cavity sizes given by related M8S16 and M12S24 hosts decrease largely the interaction toward benzene, quenching effective sequestering capabilities. Thus, the size of ten-metal cavities is proper for further fixation of benzene into metal–organic active sites. Calculated nuclear magnetic patterns suggest a deshielding shift for incorporated arene units, which are useful features to probe diffusion and orientation of the incoming VOCs. Thus, exploration of group X tiara-like structures may stimulate further applications toward sensing and treatment of different VOC species for designing versatile MOFs.